EP1831190A2

EP1831190A2 - Chroman derivatives and use thereof in liquid crystal media

Info

Publication number: EP1831190A2
Application number: EP05796927A
Authority: EP
Inventors: Markus Klein; Peer Kirsch; Eike Poetsch; Michael Heckmeier; Peter Best; Andreas Taugerbeck; Melanie Klasen-Memmer
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2004-10-07
Filing date: 2005-09-28
Publication date: 2007-09-12
Also published as: KR20070074595A; EP2258695A3; EP2258695B1; EP2258695A2; TW200630465A; JP2008522958A; US20080020148A1; WO2006040009A2; WO2006040009A3

Abstract

The invention relates to chroman derivatives of general formula (I) and (II) and chromene derivatives of formula (Ill), (IV), (V) and (VI), where R1, R2, A1, A2, Z1, Z2, L1, L2, L3, L4, m and n have the meanings relating to each formula as given in claim 1, method for production and use thereof as component(s) in liquid crystal media and liquid crystal and electrooptical display elements containing said liquid crystal media.

Description

Chroman derivatives, processes for their preparation and their

use

The present invention relates to chroman derivatives, processes for their preparation and their use as component (s) in liquid-crystalline media. Moreover, the present invention relates to liquid crystal and electro-optical display elements containing the liquid-crystalline media of the invention.

The liquid-crystalline compounds according to the invention can be used as component (s) of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of upright phases DAP or ECB (Electrically Controlled Birefringence), based on the IPS effect (In Plane Switching) or the effect of dynamic dispersion.

Benzo-fused oxygen heterocycles are suitable components for liquid crystalline mixtures that can be used in liquid crystal and electro-optic display elements.

Thus, dihydrobenzofuran and chroman derivatives become the following formula

disclosed as components of liquid crystalline mixtures in JP 06/256337, wherein R ¹ , R ² , X, Y, Z, m and n have the meanings given in this document. Chromanderivatθ the following formula

as components of liquid-crystalline mixtures are disclosed in JP 06/256339, wherein R ¹ , R ² and X have the meanings given in this document _{1 0} .

In addition, the above documents disclose processes for the preparation of benzofuran and chroman derivatives.

15

It is an object of the present invention to find novel stable, liquid-crystalline or mesogenic compounds which are suitable as component (s) of liquid-crystalline media, in particular for TN, STN, IPS, TFT and VA displays.

20

In addition, it was an object of the present invention to provide flüssig¬ crystalline compounds having a high dielectric anisotropy Δε, and depending on the substitution either positive or negative. In addition, the invention should

₂₅ compounds thermally, chemically and photochemically stable. Furthermore, the compounds according to the invention should have the broadest possible nematic phase and should be miscible with nematic base mixtures, especially at low temperatures.

₃₀ Surprisingly it was found that chromane derivatives of the invention excellent liquid-crystalline component (s) are suitable media. With their help, it is possible to obtain stable, liquid-crystalline media, in particular suitable for TFT or STN displays. The compounds of the invention are both thermal and

_{O (} - UV-stable, they are also characterized by high dielectric anisotropies Δε, which results in lower thresholds in the application. voltages are required. In addition, the compounds according to the invention have a broad nematic phase range as well as a high voltage holding ratio. Another advantage is the good solubility of the compounds of the invention, due to which they are particularly suitable for increasing the

Low temperature stability of polar liquid crystal mixtures.

By suitable choice of the ring members and / or the terminal substituents, the physical properties of the liquid crystals according to the invention can be varied within wide limits.

Since the chroman unit is in its length between that of the conventional six-membered 1- and 2-Kemer, the erfindungs¬ derivatives according to the invention also characterized by positive elastic properties.

Liquid-crystalline media with very low optical anisotropy values are of particular importance for reflective and transflective applications, i. Such applications in which the respective LCD experiences no or only supportive backlight.

With the provision of the chroman derivatives according to the invention, the range of liquid-crystalline substances which are suitable from various application-technical points of view for the preparation of liquid-crystalline mixtures is quite generally broadened considerably.

The chroman derivatives of the invention have a wide range of applications. Depending on the choice of substituents, these compounds may serve as base materials from which liquid crystalline media are predominantly composed. However, liquid-crystalline base materials from other classes of compounds may also be added to the compounds according to the invention in order, for example, to influence the dielectric and / or optical anisotropy of such a dielectric and / or to optimize its threshold voltage and / or its viscosity. The chroman derivatives according to the invention are colorless in the pure state and form liquid-crystalline mesophases in a temperature range which is favorably located for the electro-optical application. Chemically, thermally and against light, they are stable.

The present invention thus provides chroman derivatives of the general formula (I)

wherein

R ¹ H, halogen (F, Cl, Br, I), a linear or branched, optionally chiral, unsubstituted, a simply by CN or CF ₃ or at least one halogen-substituted alkyl radical having 1 to 15 carbon atoms or alkenyl radical 2 to 15 C atoms, wherein also one or more CH ₂ groups are each independently of one another by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O -, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C- or may be replaced by heteroatoms are not directly linked,

R ^{k is} H, F, Cl, NCS, CN, SF ₅ , an alkyl or alkoxy radical having 1 to 15 C atoms, an alkenyl or alkenyloxy radical having 2 to 15 C atoms, an alkyl radical which is substituted by one or more fluorine atoms or alkoxy radical having 1 to 15 C atoms or an alkenyl or alkenyloxy radical having 2 to 15 C atoms substituted by one or more fluorine atoms,

A ¹ , A ^{2 are} each independently, the same or different a) trans-1,4-cyclohexylene, in which also one or more non-adjacent CH ₂ groups can be replaced by -O- and / or -S-,

b) 1,4-phenylene, in which one or two CH groups may be replaced by N and in which also one or more H atoms may be replaced by F,

c) a radical from the group 1, 4-bicyclo (2,2,2) octylene,

Piperidine-1, 4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or

d) 1,4-cyclohexenylene,

Z ¹ , Z ^{2 are} each, independently of one another, the same or different -O-,

-CH ₂ O-, -OCH ₂ -, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ O-, -OCF ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF- , -CF = CF-CO-O-,

-O-CO-CF = CF-, -C≡C- or a single bond,

L ¹ , L ² , L ^{3 are} each independently, same or different H, F,

Cl, NCS, CN, SF ₅ , an alkyl or alkoxy radical having 1 to 15 C atoms substituted by one or more fluorine atoms or an alkenyl or alkenyloxy radical having 2 to 15 C atoms substituted by one or more fluorine atoms, preferably H, F, Cl or CN, and particularly preferably H or F,

m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3 and particularly preferably 0, 1 or 2, and

n is 1, 2, 3 or 4, preferably 1, 2 or 3 and more preferably 1 or 2, but with the proviso that the sum (m + n) = 1, 2, 3 or 4, preferably 1, 2 or 3 and more preferably 1 or 2,

and the general formula (II)

wherein R ¹ , A ¹ and Z ^{1 have} the meanings given in relation to formula (I),

L ¹ , L ² , L ³ and L ⁴ each independently, identically or differently H, F, Cl, NCS, CN, SF ₅ , a substituted by one or more fluorine atoms alkyl or alkoxy radical having 1 to 15 carbon atoms or a substituted by one or more fluorine atoms alkenyl or Alkenyloxyrest having 2 to 15 carbon atoms, preferably H, F, Cl or CN, and particularly preferably H or F, wherein

one of the two radicals L ² and L ³ additionally can also assume the meaning of R ² with respect to formula (I) and

L ² and L ³ together too

/ ⁰ X / ¹ - or Λ ⁶ , and L ^b and L ^{b are} each independently, identically or differently H, F, Cl or CN and one of the two radicals additionally also - (Z ² -A ² -) _n R ² ,

but with the proviso that when L ⁵ and L ^{6 are} each independently, identically or differently H, F, Cl or CN, m = 1, 2, 3 or 4, preferably 1, 2 or 3 and most preferably 1 or 2 is, and that when one of the two radicals - (Z ² -A ² -) _n R ² , m and n are each independently, identically or differently 0, 1, 2, 3 or 4, wherein the sum (m + n) = 1, 2, 3 or 4, preferably 1, 2 or 3,

and chromene derivatives of the general formulas (III) and (IV)

in which R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² , L ³ , m and n have the meanings given in relation to formula (I),

and chromene derivatives of the general formulas (V) and (VI)

wherein R ¹ , A ¹ , Z ¹ , L ¹ , L ² , L ³ , L ⁴ and m have the meanings given in relation to formula (II).

Preference is given to the chroman derivatives of the general formulas (I) and (II).

Another object of the present invention is the use of chroman derivatives of the formulas (I) and (II) and chromene derivatives of the formulas (III) to (VI) as component (s) in liquid-crystalline media.

Likewise provided by the present invention are liquid-crystalline media having at least two liquid-crystalline components which contain at least one chroman and / or chromene derivative of the formulas (I) to (VI).

The present invention also provides liquid-crystal display elements, in particular electro-optical display elements, which contain a liquid-crystalline medium according to the invention as a dielectric.

In a preferred embodiment, the compounds of the formula (I) to (VI) according to the invention have a negative Δε. Due to the negative Δε, these compounds are particularly suitable for use in VA displays.

The present invention thus also relates in particular to VA TFT displays with dielectrics which contain at least one chroman derivative and / or chromene derivative of the formulas (I) to (VI) with negative Δε. In a further preferred embodiment, the compounds of the formula (I) to (VI) according to the invention have a positive Δε. Due to the positive Δε, these compounds are particularly suitable for use in highly polar mixtures.

The present invention thus also relates in particular to TFT displays with a low threshold voltage (so-called "low-V _th TFT displays") and IPS displays (so-called "in plane switching displays"), with dielectrics having at least one chroman - And / or chromene derivative of the formulas (I) to (Vl) with positive Δε included.

If the compounds of the formula (I) to (VI) according to the invention additionally have a low birefringence Δn in addition to a positive Δε, these compounds are suitable in particular for use in reflective and transflective liquid crystal display elements and other low birefringence liquid crystal displays Δn, so-called "low Δn mode displays", such as reflective and transflective TN displays.

The present invention thus also relates in particular to reflective and transflective TN displays with dielectrics which contain at least one chroman and / or chromene derivative of the formulas (I) to (VI) with a positive Δε.

In addition, the chroman and chromene derivatives of the formulas (I) to (VI) according to the invention with positive Δε find use as polar clarifiers in displays which are operated at a temperature at which the control media are in the isotropic phase or in an optically isotropic phase Phase present. Such displays are e.g. in DE-A-102 17 273, DE-A-102 53 325, DE-A-102 53 606 and DE-A-103 13 979.

The meaning of formulas (I) to (VI) includes all isotopes of the chemical elements bound in the compounds of formulas (I) to (VI). In enantiomerically pure or enriched form are the Compounds of the formulas (I) to (VI) also as chiral dopants and in general for the achievement of chiral mesophases.

Above and below, R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , m and n have the meanings indicated, if not expressly stated otherwise. If the radicals A ¹ and Z ¹ and also A ² and Z ^{2 occur more} than once, they may independently of one another take on the same or different meanings.

For the sake of simplicity, in the following, Cyc means a 1, 4

Cyclohexylene radical, Che is a 1,4-cyclohexenylene radical, Dio is 1,3-dioxane-2,5-diyl radical, Thp is a tetrahydropyran-2,5-diyl radical, di-1, 3-dithian-2,5-diyl radical, Phe a 1, 4-phenylene radical, Pyd is a pyridine-2,5-diyl radical, Pyr is a pyrimidine-2,5-diyl radical, Bco is a bicyclo- (2,2,2) -octylene radical and Dec is a decahydronaphthalene radical, where Cyc and / or Phe unsubstituted or mono- or polysubstituted by -CH ₃ , -Cl, -F and / or -CN may be substituted.

Preference is given to compounds of the formulas (I) to (VI) in which R ^{1 is} H, a linear alkyl or alkoxy radical having 1 to 10 C atoms or a linear alkenyl or alkenyloxy radical having 2 to 10 C atoms.

If R ^{1 is} halogen, it preferably means F or Cl, more preferably F.

Preference is given to compounds of the formulas (I) to (VI) in which R ^{2 is} F, Cl, CN, SF ₅ , CF ₃ , OCF ₃ or OCHF ₂ , particularly preferably F, CN, CF ₃ or OCF ₃ and in particular F ,

A ¹ and A ^{2 are} preferably Phe, Cyc, Che, Pyd, Pyr or Dio, and particularly preferably Phe or Cyc. Further preferred compounds of the formulas (I) to (VI) which contain no more than one of the radicals Dio, Dit, Pyd, Pyr or Bco.

Phe is preferable

Phe is especially preferred

The terms 1, 3-dioxane-2,5-diyl and Dio each include the two positional isomers

The cyclohexene-1,4-diyl group preferably has the following structures:

Z ¹ and Z ^{2 are} preferably -CH ₂ CH ₂ -, -CH = CH-, -C≡C-, -CF ₂ CF ₂ -, -CF = CF-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ - or a single bond, more preferably -CF ₂ O-, -COO- or a single bond.

1 L _1, L2 _1, L3, L4 _1, L5 and L is preferably H or F.

Preferred chroman derivatives of the general formula (I) are the following formulas (Ia) to (Id):

wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² , L ³ , m and n have the meanings given in relation to formula (I).

Particularly preferred are the chroman derivatives of the general formulas (Ia) and (Ib).

Preferred chroman derivatives of the general formula (Ia) are the following formulas (Ia1) to (Ia6): wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (I).

Particularly preferred are the chroman derivatives of the general formulas (Ia1) to (Ia5), ie chroman derivatives of the general formula (Ia) in which m = 0 or 1.

Further preferred are chroman derivatives of the general formulas (Ia1) to (Ia6) in which L ³ = H and L ¹ and L ² independently of one another, identically or differently, denote H or F, it being particularly preferred if L ¹ = L ² = F, L ¹ = H and L ² = F or L ¹ = L ² = H.

A particularly preferred compound of sub-formula (Ia1) is that of sub-formula (Ia1a):

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ , L ² , L ³ and L ⁴ independently of one another, identically or differently, denote H or F.

Particularly preferred compounds of sub-formula (Ia2) are those of sub-formula (Ia2a) to (Ia2c):

wherein R ¹ and R ² are the meanings given in relation to formula (I) a and LL ¹¹ ,, LL ²² , LL ³³ , LL ⁴⁴ , LL ⁵⁵ and LL ⁶⁶ independently of one another, the same or different H or F mean.

A particularly preferred compound of sub-formula (Ia3) is that of sub-formula (Ia3a):

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ and L ⁸ independently, identically or differently H or F. mean.

Particularly preferred compounds of sub-formula (Ia4) are those of sub-formulas (Ia4a) to (Ia4c):

(Ia4a)

Particularly preferred compounds of the sub-formula (Ia5) are those of the sub-formulas (Ia5a) to (Ia5i), in particular those of the sub-formulas (Ia5a) to (Ia5c),

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ independently, identically or differently mean H or F.

Preferred chroman derivatives of the general formula (Ib) are the following formulas (IbI) to (Ib6):

wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (I).

Particularly preferred are the chroman derivatives of the general formulas (Ib1), (Ib2) and (Ib4), ie chroman derivatives of the general formula (Ib) in which m = 0 or 1 and the sum (m + n ) Is 1 or 2.

Further preferred are chroman derivatives of the general formulas (Ib1) to (Ib6) in which L ³ = H and L ¹ and L ^{2 are} independently, identically or differently H or F, it being particularly preferred if at least one of Radicals L ¹ and L ² F means. In particular, L ¹ = L ² = F.

Particularly preferred compounds of sub-formula (IbI) are those of sub-formulas (IbIa) to (IbIc):

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ and L ^{2 are} independently, identically or differently H or F, particularly preferably at least one of L ¹ and L ^{2 is} F, in particular but both of the leftovers.

Particularly preferred compounds of sub-formula (Ib2) are those of sub-formulas (Ib2a) to (Ib2c):

Particularly preferred compounds of sub-formula (Ib4) are those of sub-formulas (Ib4a) and (Ib4b):

Preferred chroman derivatives of the general formula (II) are the following formulas (IIa) to (Hd):

wherein R ¹ , A ¹ , Z ¹ , L ¹ , L ² , L ³ , L ⁴ and m have the meanings given in relation to formula (II) and R ² with respect to formula (I).

Particularly preferred are the chroman derivatives of the general formulas (IIa) and (IIb).

Preferred chroman derivatives of the general formula (IIa) are the following formulas (Ila1) to (Ila3):

wherein R ¹ , A ¹ , Z ¹ , L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (II) and R ² with respect to formula (I).

Particularly preferred compounds of the sub-formula (Mal) are those of the sub-formula (IIa1a) and (Halb):

(Llala)

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ and L ² independently of one another, identically or differently, denote H or F.

Preferred chroman derivatives of the general formula (IIb) are the following formulas (I IbI) to (IIb3):

CIIbI)

Particularly preferred compounds of the sub-formula (IIb1) represent those of the sub-formulas (MbIa) and (IIbi b):

wherein R ¹ and R ^{2 have} the meanings given in relation to formula (I) and L ¹ and L ^{2 are} independently, identically or differently H or F, particularly preferably at least one of L ¹ and L ^{2 is} F, in particular but both of the leftovers. The chroman derivatives of the general formulas (Ila1) to (Ila3) preferably have the following structures:

wherein R ¹ , A ¹ and Z ¹ assume the meanings given in relation to formula (II), R ² assumes the meanings given in relation to formula (I) and m = 1, 2 or 3. The chroman derivatives of the general formulas (IIb1) to (IIb3) preferably have the following structures:

wherein R ¹ , A ¹ and Z ¹ assume the meanings given in relation to formula (II), R ² assumes the meanings given in relation to formula (I) and m = 1, 2 or 3. Preferred chroman derivatives of the general formula (Hc) is the following formula (Ilc1):

wherein R ¹ , A ¹ , Z ¹ , m and L ^{1 have} the meanings given in relation to formula (II). L ¹ is preferably F or CF ₃ . R ² assumes the meanings given in relation to formula (I).

Preferred chroman derivatives of the general formula (Hd) is the following formula (Ild1):

The compounds of the formula (II), (IIa) to (Hd) and their sub-formulas include compounds having a ring in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - of the subformulae a and b:

R ¹ -A ¹ - a R ¹ -A ¹ -Z ¹ - b

Compounds with two rings in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - of sub-formulas c to f: R ¹ -A ¹ -A ¹ - c

R ¹ -A ¹ -A ¹ -Z ¹ - d

R ¹ -A ¹ -Z ¹ -A ¹ - e

R ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ - f

and compounds with three rings in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - of the subformulae g to o:

R ¹ -A ¹ -A ¹ -A ¹ - g R ¹ -A ¹ -Z ¹ -A ¹ -A ¹ - h

R ¹ -A ¹ -A ¹ -Z ¹ -A ¹ - i

R ¹ -A ¹ -A ¹ -A ¹ -Z ¹ - j

R ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ -A ¹ - k

R ¹ -A ¹ -Z ¹ -A ¹ -A ¹ -Z ¹ - m R ¹ -A ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ - n

R ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ - o

Of these, those of sub-formulas a, b, c, d, e, g, h and i are particularly preferred.

The preferred compounds of sub-formula a include those of sub-formulas aa to ad:

R ¹ -Phe- aa R ¹ -Cyc- from

R ¹ -Thp- ac

R ¹ -Di ad

Of these, those of the following sub-formulas are particularly preferred:

The preferred compounds of sub-formula b include those of sub-formulas ba and bb:

R ¹ -Phe-Z ¹ - ba R ¹ -Cyc-Z ¹ - bb

The preferred compounds of sub-formula Ic include those of sub-formulas ca to cm:

R ¹ -Cyc-cyc

R ¹ -Cyc-Thp- cb

R ¹ -Cyc-DioCC

R ¹ -Cyc-Phe- cd

R ¹ -Thp cycle

R ¹ -Dio-Cyc-Cf

R ¹ -Phe-cyc- cg

R ¹ -Thp-Phe- ch

R ¹ -Dio-Phe- ci R -Phe-Phe- cj

R ¹ -Pyr-Phθ- ck

R ¹ -Pyd-Phθ- cm

Of these, those of the following sub-formulas are particularly preferred:

The preferred compounds of sub-formula d include those of sub-formulas da to dn:

R -Cyc-Cyc-Z - da

R ¹ -Cyc-Thp-Z ¹ -db

R ¹ -Cyc-Dio-Z ¹ - de

R ¹ -Cyc-Phe-Z ¹ - dd

R ¹ -Thp-Cyc-Z ¹ - de

R ¹ -Dio-Cyc-Z ¹ - df

R ¹ -Thp-Phe-Z ¹ - dg

R ¹ -Dio-Phe-Z ¹ - ie

R ¹ -Phe-Phe-Z ¹ - di R ¹ -Pyr-Phe-Z ¹ - dj

R ¹ -Phe-Phe-Z ¹ - dk

R ¹ -Cyc-Phe-CH ₂ CH ₂ -dm

R ¹ -A ¹ -Phe-CH ₂ CH ₂ - dn

Of these, those of the following sub-formulas are particularly preferred:

The preferred compounds of sub-formula e include those of sub-formulas ea to ej:

R -Cyc-Z -Cyc-ea

R ¹ -Thp-Z ¹ -Cyc-eb

R ¹ -A ¹ - CH ₂ CH ₂ -A ¹ - ec

R ¹ -Cyc-Z ¹ -Phe- ed

R ¹ -Thp-Z ¹ -Phe- ee

R ¹ -A ¹ -OCO-Phe- ef

R ¹ : phe-Z ¹ -phe- eg

R ¹ -Pyr-Z ¹ -A ¹ - eh R ¹ -Pyd-Z ¹ -A ¹ - eι R ¹ -Dio-Z ¹ -A ¹ - θj

Of these, those of the following sub-formulas are particularly preferred:

The preferred compounds of sub-formula f include those of sub-formulas fa to fe:

R ¹ -Phe-CH ₂ CH ₂ -A ¹ -Z ¹ - fa

R ¹ -A ¹ -COO-Phe-Z ¹ - fb

R ¹ -Cyc-Z ¹ -Cyc-Z ¹ - fc

R ¹ -Phe-Z ¹ -Phe-Z ¹ - fd

R ¹ -Cyc-CH ₂ CH ₂ -Phe-Z ¹ - fe

The preferred compounds of partial formulas g to n include those of the following partial formulas ga to ma:

R -A -cyclo- ga

R ¹ -A ¹ -Cyc-phenyl

R ¹ -Phe-Phe-Phegc

R ¹ -A ¹ -CH ₂ CH ₂ -A ¹ -Phe- ha

R ¹ -Phe-Z ¹ -A ¹ -Phe- hb

R ¹ -A ¹ -Phe-Z ¹ -Phe- ia

R ¹ -Cyc-Z ¹ -A ¹ -Z ¹ -Phe- ka

R ¹ -A ¹ -Z ¹ -Cyc-Phe-Z ¹ - ma

In the above preferred formulas, R ¹ , A ¹ and Z ^{1 have} the meanings given above. If A ¹ and / or Z ¹ occur several times in one of the subformulae, they may independently of one another be the same or different. In the above, preferred formulas, R ¹ preferably denotes a linear alkyl or alkoxy radical having 1 to 7 C atoms or a linear alkenyl or alkenyloxy radical having 2 to 7 C atoms and particularly preferably a linear alkyl radical having 1 to 7 C Atoms or a linear alkenyl radical having 2 to 7 carbon atoms.

In the above preferred formulas, Z ^{1 is} preferably -CH ₂ CH ₂ -, -C≡C-, -CF ₂ CF ₂ -, -COO-, -OCO-, -CF ₂ O- or -OCF ₂ -.

If R ¹ or R ² in the formulas above and below denotes an alkyl radical, this may be straight-chain or branched. It is particularly preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and accordingly denotes methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl, furthermore octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl or pentadecyl.

If R ¹ or R ^{2 is} an alkyl radical in which one CH ₂ group has been replaced by -O-, this may be straight-chain or branched. It is preferably straight-chain and has 1 to 10 carbon atoms. Particularly preferably, the first CH ₂ group of this alkyl radical is replaced by -O-, so that the radical R ^{1 is} alkoxy and methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or nonyloxy.

Furthermore, a CH ₂ group may be replaced elsewhere by -O-, so that the radical R ^{1 is} preferably 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-oxo-octyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8 - or 9-oxadecyl.

If R ¹ or R ^{2 is} an alkyl radical in which one CH ₂ 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. It therefore means vinyl, prop-1 or prop-2-enyl, but-1, 2- or but-3-enyl, pent-1, 2-, 3- or pent-4-enyl, hex-1 -, 2-, 3-, 4- or hex-5-enyl, Hept-1, 2-, 3-, 4-, 5- or hept-6-enyl, Oct-1, 2-, 3-, 4-, 5-, 6- or Oct-7-enyl, Non 1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, Dec-1, 2-, 3-, 4-, 5-, 6-, 7- , 8- or dec-9-enyl.

Preferred alkenyl groups are C ₂ -C ₇ -I E-alkenyl, C ₄ -C ₇ -EE-alkenyl,

C ₅ -C ₇ -alkenyl, C ₆ -C ₇ -5-alkenyl, and C ₇ -6-alkenyl, more preferably C ₂ -C ₇ -I E-alkenyl, C ₄ -C ₇ -EE-alkenyl and C ₅ -C ₇ -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 and 6-heptenyl. Groups of up to 5 carbon atoms are especially preferred.

If R ^{1 is} an alkyl radical in which one CH ₂ group has been replaced by -O- and one by -CO-, these are preferably adjacent. Thus, they include an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are particularly preferably straight-chain and have 2 to 6 C atoms.

Accordingly, they particularly mean acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyl-oxyethyl, 2-butyryloxyethyl, 3-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 and 4- (methoxycarbonyl) butyl.

If R ^{1 is} an alkyl radical in which 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-, so this can be straight-chain or branched. Preferably, it is straight-chain and has 4 to 13 carbon atoms. He therefore means particularly preferred Acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyi, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4- Methacryloyloxybutyl, 5-methacryloyloxypentyl,

6-methylthacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl and 9-methacryloyloxynonyl.

If R ¹ is a monosubstituted by CN or CF ₃ alkyl or alkenyl radical, this radical is preferably straight-chain and the substitution by CN or CF ₃ in ω-position.

If R ¹ or R ^{2 is} an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain. Halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F. The resulting radicals also include perfluorinated radicals. For single substitution, the fluoro or chloro substituent may be in any position, but preferably in the ω position.

Compounds of the formulas (I) to (VI) with branched wing group R ¹ or R ² may occasionally be of importance for better solubility in the customary liquid-crystalline base materials, but especially as chiral dopants, if they are optically active. Smectic compounds of this type are useful as component (s) for ferroelectric materials.

Branched groups of this type preferably contain no more than one chain branch. Preferred branched radicals R ¹ or R ² are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl),

2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentyloxy, 3 Methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methylheptyloxy. The formulas (I) to (VI) include both the racemates of these compounds and the optical antipodes and mixtures thereof.

Among the compounds of the formulas (I) to (VI) and the sub-formulas, preference is given to those in which at least one of the radicals contained therein has one of the preferred meanings indicated.

In the compounds of the formulas (I) to (VI), preference is given to those stereoisomers in which the rings cyc and piperidine are trans-1,4-disubstituted. Those of the above formulas containing one or more groups Pyd, Pyr and / or Dio each include the two 2,5-position isomers.

The compounds of the general formulas (I) to (VI) can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart) are under reaction conditions which are known and suitable for the reactions mentioned. One can make use of known per se, not mentioned here variants.

The starting materials for the above processes are either known or can be prepared in analogy to known compounds. They are thus available according to generally available literature regulations or commercially available.

If desired, the starting materials can also be formed in situ, such that they are not isolated from the reaction mixture, but immediately further reacted to give the compounds of the general formulas (I) to (VI).

A preferred synthesis of the compounds of the general formulas (Ib) and (III) can be carried out according to the methods described in the literature, for example in Houben Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, New York, 4.Aufl. 1993, described methods. A preferred process is the preparation of compounds of general formula (Ib) by ring-closing metathesis of the appropriately substituted dienes 3, which are available according to S. Chang, RH Grubbs, J. Org. Chem. 1998, 63, 864-866. The chromenes of the general formula (III) thus obtained can be converted by catalytic hydrogenation to the chromans of the general formula (Ib), as shown in Scheme 1.

Scheme 1

Chroman synthesis by metathesis

Alternatively, the compounds of general formula (Ib) according to the invention may also be obtained by intramolecular cyclization of diols, e.g. by S. Kelly, B.C. Vanderplas, in J. Org. Chem. 1991, 56, 1325-1327 and shown in Scheme 2.

By aldol condensation of the salicylaldehyde derivatives 4 with methyl ketones and subsequent hydrogenation and removal of the protective group, the ketones 5 are obtained, which after reduction to the alcohol 6, e.g. with sodium borohydride and by subsequent treatment with sulfuric acid in glacial acetic acid to the compounds of formula (Ib) cyclize.

Scheme 2

Chromansynthesis by etherification

Salicylaldehydes can be used as starting material for compounds 3 and 4. One possible method of preparing these salicylaldehydes is the reaction of commercial liquid crystal precursors 7 according to Scheme 3 below.

Scheme 3

Preparation of fluorosalicylaldehydes

After conversion of the phenols 7 into a suitable derivative, for example MOM ether 8, the salicylaldehydes 9 can be obtained directly by ortho-metalation, trapping with a formamide derivative such as DMF and subsequent deprotection, for example by LR. Hardcastle, P. Quayle, ELM Ward in Tetrahedron Lett. 1994, 35, 1747-1748.

Alternatively, the phenols 7 may also be first halogenated and then metalated after protection of the hydroxyl group by halogen-lithium exchange and reacted analogously to Scheme 4 to salicylaldehydes, e.g. from G.G. Finger, MJ. Gortakowski, R.H. Shiley, R.H. White in J. Amer. Chem. Soc. 1959, 81, 94-101 and shown in Scheme 4.

Scheme 4

The preparation of the chroman derivatives of the general formula (II) according to the invention is preferably carried out by reacting

a) an oxetane of the general formula (VIIa) or (VIIb)

wherein R ¹ , A ¹ , Z ¹ and m have the meanings given in relation to formula (II), with a fluorinated in ortho position fluoroaromatics in an organic solvent and at low temperatures to the corresponding propanol derivative of the general formula (Villa) or (VIIIb) implements,

villa

VIIIb

wherein R ¹ , A ¹ , X ¹ , X ² , X ³ , X ⁴ , Z ¹ and m have the meanings given in relation to formula (II), and

b) the propanol derivative of the general formula (Villa) or (VIIIb) formed is cyclized by the action of a strong, non-nucleophilic base to give the corresponding chroman derivative of the general formula II.

The chroman derivative obtained in this way can optionally be converted by dehydrogenation to the corresponding chromene derivative.

The reaction in step a) preferably takes place in the presence of a Lewis acid. As Lewis acids, it is possible in principle to use all compounds known to the person skilled in the art, provided that they have no acidic protons. Particularly preferred are strong Lewis acids, in particular BF ₃ etherate. In the case of particularly reactive compounds, the reaction can also be carried out without the addition of a Lewis acid.

As organic solvents, all solvents suitable for this purpose can be used in step a). Preferred as

However, solvents are diethyl ether, tetrahydrofuran (THF) and dimethoxyethane (DME) and mixtures thereof.

By low temperature is meant in the present application, a temperature in the range of -4O ° C to -100 ° C, preferably from -65 ° C to -85 ° C.

The preparation of the oxetanes can be carried out according to all methods known in the art. Preferably, however, starting from diols of the following formulas, which are either commercially available or are easy to prepare. A process for their preparation is described e.g. in EP 0 967 261 B1. These diols can then be converted into oxetanes, for example, by the method described by Picard et al., Synthesis, 1981, 550-552, as shown in Scheme 5 below.

Scheme 5

The preparation of the ortho-metallated fluoroaromatics can also be carried out by all methods known to the person skilled in the art. However, preferred methods are the ortho-metallation of fluoroaromatics with butyllithium (BuLi), optionally with the addition of TMEDA or similar compounds for increasing the reactivity of the aggregated butyllithium, Schlosser-Lochmann base or lithium diisopropylamide (LDA) in each case at low temperatures or the halogen-metal exchange of iodine fluoroaromatics or bromine fluoroaromatics with BuLi at low temperatures (for example according to Org. React. 6, 1951 , 339-366) or iso-propylmagnesium chloride

Temperatures in the range of -50 ° C to -1O ° C (Knöchel et al., Angewandte Chemie, Int Ed. 42, 2003, 4302-4320).

Optionally, this step can also be followed by a re-metallization. For example, lithium aromatics can be easily converted into the corresponding zinc aromatics by reaction with a ZnCl ₂ solution.

The ortho-metalated fluoroaromatic is then reacted with the oxetane in an organic solvent at low temperature, preferably in the presence of a Lewis acid as shown in Schemes 6a and 6b.

Depending on the oxetane used, the structurally isomeric alcohols can also be obtained in this way.

The opening of the oxetane takes place with high regioselectivity on the less substituted side.

Scheme 6a

Scheme 6b

The propanol derivative formed from the ortho-metalated fluoroaromatic and oxetane is then reacted in the presence of about 1 equivalent of a strong, non-nucleophilic base, e.g. Alkali hydride selected from NaH, KH, RbH or CsH, and potassium hexamethyldisilazane (KHMDS), preferably alkali metal hydride, more preferably KH, intramolecularly cyclized in an organic solvent. The reaction is shown in Scheme 7 below. Preferably, this cyclization takes place in a temperature range between 0 ° C and 78 ° C. Particularly preferred is the use of 1 to 1.5 equivalents of potassium hydride (KH) in tetrahydrofuran (THF).

The products obtained in this way may optionally be reused as starting materials. In this way, with suitable fluorine substitution, it is also possible to build up compounds according to the invention having two heterocycles, as shown in the two reaction schemes 8a and 8b above.

The cyclization reactions may be followed by further reactions, e.g. the functionalization of the aromatic radical by introduction of further halogen substituents, such as chlorine, bromine or iodine, or by introduction of boronic acid groups by literature methods.

Corresponding reaction examples show the following scheme 9:

A preferred synthesis for the construction of aryl-substituted fluoro-benzochroman derivatives of the general formula (Ia) is carried out by Suzuki coupling of corresponding boronic acids or boronic acid esters with 7-bromo-8-fluoro-chromans or 7-bromo-6,8-difluoro-chromans according to the following scheme 10. The required boronic acid derivatives are prepared from bromine-substituted precursors by known methods, as disclosed, for example, in J. Org. Chem. 1995, 60, 7508-7510. The synthesis can be adapted by the choice of suitable starting materials to the particular desired compounds of general formula (Ia). That way you can among others, the particularly preferred compounds of the subformulae (IIIa) and (Ia2b) represent.

Scheme 10

The reactions shown are only to be considered as exemplary. The person skilled in the art can carry out corresponding variants of the syntheses presented, as well as other suitable synthetic routes, in order to obtain the compounds of the formulas (I) to (VI) according to the invention.

The syntheses of various chroman derivatives according to the invention are also described by way of example in the examples.

The present invention also provides liquid-crystalline media comprising in addition to one or more compounds of the formulas (I) to (VI) 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-tetrahydropyrans, phenyl or cyclohexyl benzoates, cyclohexane. phenylcyclohexyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes,

Cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-biscyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyl-dioxanes, phenyl- or cyclohexyl-1,3 -dithiane, 1, 2-diphenylethane, 1, 2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) -ethanes, 1-cyclohexyl-2-biphenylethane, 1-phenyl -2- cyclohexylphenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1, 4-phenylene groups in these compounds can also be mono- or polyfluorinated.

The most important compounds which may be used as further constituents of the media according to the invention can be characterized by the formulas 1, 2, 3, 4, 5 and 6:

R'-L-E-R "1

R'-L-COO-E-R "2

R'-L-OOC-E-R "3

R'-L-CH ₂ CH ₂ -ER "4 R'-LC≡CER" 5

R'-L-CFao-E-R "6

In the formulas 1, 2, 3, 4, 5 and 6, L and E, which may be identical or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe- , -Phe-Cyc, -Cyc-Cyc, -Pyr-, -Dio, -Thp-, -G-Phe- and -G-Cyc- and their mirror images formed group, wherein Phe is unsubstituted or substituted by fluorine 1 , 4-phenylene, cyc trans-1, 4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dioio-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.

Preferably, one of L and E is Cyc or Phe. E is preferably Cyc, Phe or Phe-Cyc. Preferably, the inventive media contain one or more components selected from the compounds of formulas 1, 2, 3, 4, 5 and 6, wherein L and E are selected from the group Cyc and Phe and simultaneously one or more components selected from the Compounds of the formulas 1, 2, 3, 4, 5 and 6, wherein one of the radicals L and E is selected from among

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 more Components selected from the compounds of the formulas 1, 2, 3, 4, 5 and 6, wherein the radicals L and E are selected from the group -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G -Cyc-.

R 'and / or R "are each independently of one another alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms, -F, -Cl, -CN, -NCS, - (O) _i CH _{3 (K + I)} F _k Cl _I , where i is 0 or 1, k and I are independently, the same or different, 0, 1, 2 or 3, but with the proviso that the sum (k + I) 1, 2 or 3 is.

R 'and R "each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms in a smaller subgroup of the compounds of formulas 1, 2, 3, 4, 5 and 6 This smaller subgroup is called group A and the compounds are denoted by the subformulae 1a, 2a, 3a, 4a, 5a and 6a In most of these compounds, R ¹ and R "are different from one another, one of these radicals usually being alkyl, alkenyl Is alkoxy or alkoxyalkyl.

In the smaller subgroup of the compounds of the formulas 1, 2, 3, 4, 5 and 6 designated as group A, E in a preferred embodiment

In a smaller subgroup of the compounds of the formulas 1, 2, 3, 4, 5 and 6 designated as group B, R "is -F, -Cl, -NCS or - (O) i CH ₃ - _{(k +} | ₎ F _k CI |, where i is 0 or 1, k and I are independently 0, 1, 2 or 3, but with the proviso that the sum (k + I) is 1, 2 ^ Q or 3. The compounds in which R "has this meaning are designated by the sub-formulas 1b, 2b, 3b, 4b, 5b and 6b. Particular preference is given to those compounds of the subformulae 1 b, 2b, 3b, 4b, 5b and 6b in which R "has the meaning -F, -Cl, -NCS, -CF ₃ , -OCHF ₂ or -OCF ₃ .

15

In the compounds of the subformulae 1 b, 2b, 3b, 4b, 5b and 6b, R ^{1 has} the meaning given for the compounds of the subformulae 1a to 6a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.

In a further smaller subgroup of the compounds of the formulas 1, 2, 3, 4, 5 and 6, R "denotes -CN. This subgroup is referred to below as group C and the compounds of this subgroup are correspondingly assigned with partial formulas 1c, 2c, 3c 4c, 5c and 6c In the compounds of the subformulae 1c, 2c, 3c, 4c, 5c and 6c, R ^{1 has} the meaning given for the 5 compounds of the subformulae 1 a to 6a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl ,

In addition to the preferred compounds of groups A, B and C, other compounds of the formulas 1, 2, 3, 4, 5 and 6 with other variants of the substituents provided are also customary. All these

Substances can be obtained by methods known from the literature or in analogy thereto.

The media according to the invention contain, besides the inventive ₅ compounds of formulas (I), (II), (III), (IV), (V) and / or (VI) is preferably one or more compounds selected are from the groups A ₁ B and / or C. The mass fractions of the compounds from these groups in the media according to the invention are preferably:

Group A: 0 to 90%, preferably 20 to 90%, particularly preferably 30 to 90%; Group B: 0 to 80%, preferably 10 to 80%, particularly preferably 10 to 70%; Group C: 0 to 80%, preferably 5 to 80%, particularly preferably 5 to 50%;

wherein the sum of the mass fractions of the compounds of the groups A, B and / or C contained in the respective erfindungs¬ contemporary media is preferably 5 to 90% and particularly preferably 10 to 90%.

The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of the compounds according to the invention. Furthermore preferred are media containing more than 40%, particularly preferably 45 to 90%, of compounds according to the invention. The media preferably contain one, two, three, four or five compounds of the invention.

Examples of the compounds of the formulas 1, 2, 3, 4, 5 and 6 are the compounds listed below:

with R ^a , R ^b independently of one another -CpH _{2p + 1} or -OCpH _{2p + 1} and p = 1, 2,

3, 4, 5, 6, 7 or 8 and L ¹ , L ^{2 are} independently -H or -F,

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

The preparation of the liquid-crystal mixtures according to the invention is carried out in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the main component, preferably 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 after thorough mixing, for example by distillation. Furthermore, it is possible to use the mixtures in other conventional ways, for example by using premixes, for example homolog mixtures or using so-called "multi-bottle" systems.

The dielectrics may also other, known in the art and in the

Literature described additives contain. For example, 0 to 15%, preferably 0 to 10%, of pleochroic dyes and / or chiral dopants may be added. The individual compounds added are used in concentrations of from 0.01 to 6%, preferably from 0.1 to 3%. However, the concentration data of the other constituents of the liquid-crystal mixtures, ie of the liquid-crystalline or mesogenic compounds, are given without consideration of the concentration of these additives.

In the present application and in the following examples, the structures of the liquid-crystal compounds are indicated by acronyms, wherein the transformation into chemical formulas according to the following tables A and B takes place. All radicals C _n H _{2n + I} and C _m H _{2m +} i are straight-chain alkyl radicals with n or m C atoms. n and m are integers, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, where n = m or n ≠ m. The coding according to Table B is self-evident. In Table A, only the acronym for the main body is given. In individual cases, a code for the substituents R ^{1 *} , R ^{2 *} , L ^{1 *} and L ^{2 *} follows separately from the acronym for the main body with a dash ^:

Code for R ^{1 *} , R ^{1 *} R ² L ¹ L ²

R ^{2 *} , L ^{1 *} , L ^{2 *}

Preferred mixture components are given in Tables A and B.

Table A:

Table B:

Table C:

In Table C possible dopants are given, which are preferably added to the mixtures according to the invention.

Particular preference is given to mixtures according to the invention which, in addition to one or more compounds of the formulas (I), (II), (III), (IV), (V) and / or (VI), two, three or more compounds selected from Tables A and / or B included.

The following examples are intended to illustrate the invention without limiting it. Above and below, percentages are by weight. All temperatures are in degrees Celsius. Tg is the

Glass transition temperature and KIp. is the clearing point. Furthermore, K = crystalline state, N = nematic phase, Sm = smectic phase and I = isotropic phase. The data between these symbols represent the transition temperatures. Δn means optical anisotropy (589 nm, 20 ° C) ₁ Δε the dielectric anisotropy (1 kHz, 20 ° C) and Y ₁ the rotational viscosity at 20 ° C [mPas]. The Δn and Δε values of the compounds according to the invention were obtained by extrapolation from liquid-crystalline mixtures which consist of 10% of the respective compound according to the invention and 90% either of the commercially available liquid crystal ZLI 4792 (Δn and positive Δε values) or also commercially available liquid crystal ZLI 2857 (negative Δε values), both Fa. Merck, Darmstadt, passed.

The following abbreviations are used above and below:

AIBN Azoisobutyronitrile

BuLi Butyllithium

DCM dichloromethane

EE vinegar

KH potassium hydride

KHMDS potassium hexamethyldisilazane

LDA lithium diisopropylamide

MCPBA 3-chloroperoxybenzoic acid

MTBE tert-butyl methyl ether

NBS N-bromosuccinimide

RT room temperature

THF tetrahydrofuran

TMEDA tetramethylethylenediamine

Example 1 7,8-Difluoro-6- (4-trans-pentyl-cyclohexyl) -chroman

1st stage: 2-Allyloxy-3,4-difluoro-5- (4-trans-pentylcyclohexyl) benzaldehyde

3.00 g (9.67 mmol) of 3,4-difluoro-2-hydroxy-5- (4-pentylcyclohexyl) benzaldehyde are dissolved in 30 ml of acetone and after addition of 2.1 g (15 mmol) of potassium carbonate and 2.5 ml (30 mmol) of allyl bromide heated at 60 [deg.] C. for 3 hours. After filtration, the filtrate is concentrated and the residue purified by chromatography with heptane / MTB ether (50: 1) on silica gel. 3.23 g (95%) of 2-allyloxy-3,4-difluoro-5- (4-pentylcyclohexyl) benzaldehyde are obtained as colorless crystals.

2nd Step: 2-Allyloxy-3,4-difluoro-5- (4-trans-pentylcyclohexyl) -1-vinylbenzene

3.66 g (10.0 mmol) of methyltriphenylphosphonium bromide are initially charged in 20 ml of THF and, while cooling with ice, 1.15 g (10.0 mmol) of potassium tert-butoxide are added. After 10 minutes, a solution of 3.23 g (9.22 mmol) of 2-allyloxy-3,4-difluoro-5- (4-pentylcyclohexyl) benzaldehyde in 15 ml of THF is added dropwise. The cooling is removed, the mixture is allowed to stir for 2 hours at room temperature and added to ice-water. The aqueous phase is separated and extracted three times with MTB ether. The combined organic phases are washed with water and saturated sodium chloride solution and concentrated in vacuo. The residue is taken up in heptane and with heptane / MTB ether (50: 1) filtered through silica gel. This gives 2.71 g (84%) of 2-allyloxy-3,4-difluoro-5- (4-pentyl-cyclohexyl) -1-vinyl-benzene as a colorless oil.

3rd stage: 7,8-Difluoro-6- (4-trans-pentyl-cyclohexyl) -2H-chromene

2.68 g of 2-allyloxy-3,4-difluoro-5- (4-trans-pentyl-cyclohexyl) -1-vinyl-benzene are dissolved under nitrogen in 40 ml of dichloromethane and after addition of 63 mg of Grubbs' catalyst for 2 hours stir at room temperature. The mixture is concentrated and the residue is chromatographed on silica gel with n-heptane / MTB ether (50: 1). This gives 930 mg (38%) of 7,8-difluoro-6- (4-pentyl-cyclohexyl) -2H-chromene as colorless crystals.

4th Step 7,8-Difluoro-6- (4-trans-pentyl-cyclohexyl) -chroman

930 mg of 7,8-difluoro-6- (4-pentylcyclohexyl) -2H-chromene are hydrogenated in ethanol on palladium-activated carbon (5%) at 1 bar and room temperature to standstill. The catalyst is filtered off, the filtrate is concentrated and the residue is recrystallized from ethanol. This gives 680 mg (79%) of 7,8-difluoro-6- (4-trans-pentyl-cyclohexyl) -chroman as colorless crystals of mp. 49 ° C. Δε. = -3.2 Δn = 0.0685 Example 2 2-Ethyl-6- (4-trans-ethyl-cyclohexyl) -7,8-difluoro-chroman

1st stage: 2,3-Difluoro-4- (4-trans-ethylcyclohexyl) -6-vinyl-phenol

26.5 g (74.4 mmol) of methyltriphenylphosphonium bromide are initially charged in 150 ml of THF and, with ice-cooling, a solution of 8.33 g (74.2 mmol) of potassium tert-butoxide in 50 ml of THF is added dropwise. After 2 hours, 30.0 g (67.5 mmol) of 3,4-difluoro-2- (2-methoxy-ethoxymethoxy) -5- (4-trans-ethyl-cyclohexyl) benzaldehyde in 50 ml of THF is added and over Stir at room temperature overnight. The mixture is hydrolyzed with water, 100 ml of conc. Add hydrochloric acid and stir vigorously for 3 hours. It is then extracted with MTBE, the combined extracts washed with saturated brine, dried over sodium sulfate and concentrated. This gives 16.0 g (81%) of 2,3-difluoro-4- (4-trans-ethyl-cyclohexyl) -6-vinyl-phenol as a yellow oil, which is pure enough for further reactions.

2nd step: 2- (1-ethyl-allyloxy) -5- (4-trans-ethylcyclohexyl) -3,4-difluoro-1-vinylbenzene

To a solution of 10.0 g (37.5 mmol) of 4- (4-trans-ethyl-cyclohexyl) -2,3-difluoro-6-vinyl-phenol, 11.8 g (45.0 mmol) of triphenylphosphine and 3.88 g (45.0 mmol) of 1-penten-3-ol in 150 ml of THF are added dropwise 7.84 g (45.0 mmol) of diethyl azodicarboxylate in 50 ml of THF. The mixture is stirred for 5 hours at room temperature and extracted with ethyl acetate. The United organic phases are washed with saturated sodium chloride solution and dried over sodium sulfate. The solvent is removed in vacuo and the crude product is purified by chromatography with n-heptane / ethyl acetate (20: 1) on silica gel. This gives 9.91 g (79%) of 2- (1-ethyl-allyloxy) -5- (4-trans-ethyl-cyclohexyl) -3,4-difluoro-1-vinyl-benzene as a colorless oil.

3rd stage: 2-ethyl-6- (4-trans-ethylcyclohexyl) -7,8-difluoro-2H-chromene

In analogy to the synthesis described in Example 1, in the 3rd stage, 7.50 g (22.4 mmol) of 2- (1-ethyl-allyloxy) -5- (4-trans-ethylcyclohexyl) - 3,4-difluoro-1-vinyl-benzene 5.29 g (77%) of 2-ethyl-6- (4-transethylcyclohexyl) -7,8-difluoro-2H-chromene as colorless crystals.

4th stage: 2-ethyl-6- (4-trans-ethylcyclohexyl) -7,8-difluoro-chroman

5.00 g (16.3 mmol) of 2-ethyl-6- (4-trans-ethylcyclohexyl) -7,8-difluoro-2H-chromene are dissolved in 20 ml of THF and dissolved in 20 ml of THF in the presence of palladium activated carbon catalyst Standstill hydrogenated. The solution is filtered through silica gel and the solvent removed in vacuo. 4.38 g (87%) of 2-ethyl-6- (4-trans-ethylcyclohexyl) -7,8-difluorochromane are obtained as colorless crystals.

Δε = -5.5 Δn = 0.1 12 Example 3 6- (4-ethyl-phenyl) -7,8-dif [uor-2-methyl-chroman

1st stage: 4- (4'-ethyl-5,6-difluoro-4-hydroxy-biphenyl-3-yl) -but-3-en-2-one

9.44 g (26.9 mmol) of 4'-ethyl-5,6-difluoro-4- (2-methoxyethoxymethoxy) biphenyl-3-carbaldehyde are dissolved in 50 ml of acetone, 8.5 g of 50 percent strength by weight. Sodium hydroxide solution and 300 ml of water were added and allowed to stir for 3 days at room temperature. The batch is extracted with dichloromethane, concentrated and taken up in 100 ml of THF. After addition of 30 ml of conc. Hydrochloric acid is vigorously stirred overnight and then extracted with MTBE. The combined organic phases are washed with water, dried over sodium sulfate and the solvent is removed in vacuo. Filtration with MTBE over silica gel gives 12.2 g (92%) of 4- (4'-ethyl-5,6-difluoro-4-hydroxy-biphenyl-3-yl) -but-3-en-2-one as a colorless oil.

2nd step: 4- (4'-ethyl-5,6-difluoro-4-hydroxybiphenyl-3-yl) -butan-2-one

10.1 g (33.3 mmol) of 4- (4'-ethyl-5,6-difluoro-4-hydroxy-biphenyl-3-yl) -but-3-en-2-one are dissolved in 80 ml of THF and hydrogenated on palladium-activated carbon (5%) to a standstill. It is then filtered, concentrated and the residue purified by chromatography on silica gel. This gives 7.71 g (76%) of 4- (4'-ethyl-5,6-difluoro-4-hydroxybiphenyl-3-yl) -butan-2-one as a colorless oil.

3rd step: 4'-ethyl-2,3-difluoro-5- (3-hydroxybutyl) -biphenyl-4-ol

5.8 g (19.1 mmol) of 4- (4'-ethyl-5,6-difluoro-4-hydroxybiphenyl-3-yl) -butan-2-one are dissolved in 30 ml of isopropanol, 600 mg (15, 9 mmol) sodium borohydride and stirred overnight at room temperature. The mixture is carefully acidified, diluted with 50 ml of water and extracted with MTBE. The combined organic phases are washed with water and dried over sodium sulfate. After removal of the solvent in vacuo, 4.91 g (84%) of 4'-ethyl-2,3-difluoro-5- (3-hydroxybutyl) -biphenyl-4-ol are obtained as a yellow oil, which are reacted without further purification can.

4th stage: 6- (4-ethylphenyl) -7,8-difluoro-2-methylchroman

4.5 g (14.7 mmol) of 4'-ethyl-2,3-difluoro-5- (3-hydroxybutyl) -biphenyl-4-ol are dissolved in 25 ml of glacial acetic acid and 25 ml of 50 percent strength by weight. Dissolved sulfuric acid and heated to 6O ° C for 30 minutes. The mixture is added to ice-water, neutralized with sodium hydroxide solution and extracted with MTBE. The combined organic phases are dried over sodium sulfate, concentrated and the residue is purified by chromatography on silica gel. This gives 3.05 g (72%) of 6- (4-ethyl-phenyl) -7,8-difluoro-2-methylchroman as a colorless solid. Δε = -8.7 Δn = 0.191

Example 4 7,8-Difluoro-2-methyl-6- (4-trans-propyl-cyclohexyl) -chroman

1st stage: 2,3-difluoro-6- (3-hydroxybutyl) -4- (4-trans-propylcyclohexyl) phenol

15.9 g (39 mmol) of 4- [3,4-difluoro-2- (2-methoxy-ethoxymethoxy) -5- (4-propylcyclohexyl) -phenyl] -but-3-en-2-one hydrogenated in 150 ml of tetrahydrofuran on palladium activated carbon catalyst at 4 bar and room temperature to standstill. The solution is filtered, with 150 ml of methanol and 15 ml of conc. Hydrochloric acid added and allowed to stir overnight at room temperature. The mixture is then added to water and extracted three times with MTB ether. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo and the residue is chromatographed on silica gel with heptane / MTB ether (1: 1). This gives 12.3 g (77%) of 2,3-difluoro-6- (3-hydroxy-butyl) -4- (4-propyl-cyclohexyl) -phenol as a colorless oil.

2nd Step: 7,8-Difluoro-2-methyl-6- (4-trans-propyl-cyclohexyl) -chroman

2.30 g (7.05 mmol) of 2,3-difluoro-6- (3-hydroxybutyl) -4- (4-propylcyclohexyl) phenol and 1.94 g (7.40 mmol) of triphenylphosphine dissolved in 20 ml of tetrahydrofuran and added dropwise to 1, 64 ml (8.46 mmol) of diisopropyl azodicarboxylate in 10 ml of tetrahydrofuran. The reaction is stirred overnight at room temperature, diluted with 30 ml of MTB ether and added to water. The organic phase is separated and extracted three times with MTB ether. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo and the residue is purified by chromatography using heptane / MTB ether (4: 1) on silica gel and then recrystallized from ethanol. This gives 1, 3 g (55%) of colorless crystals of mp. 69 ° C.

Δε = -7.7 Δn = 0.0759

Example 5 6- (4-trans-ethylcyclohexyl) -7,8-difluoro-2-p-tolylchroman

1st stage: 5- (4-trans-ethyl-cyclohexyl) -3,4-difluoro-2- (1-p-tolyl-allyloxy) -benzaldehyde

In analogy to the synthesis described under Example 2, Mitsunobu reaction of 3,4-difluoro-2-hydroxy-5- (4-trans-pentylcyclohexyl) -benzaldehyde and 1-p-tolyl-prop-2- en-i -ol, the 5- (4-trans-ethyl cyclohexyl) -3,4-difluoro-2- (1-p-tolyl-allyloxy) -benzaldehyde in 53 percent. Yield as a colorless solid.

2nd step: 1- (4-transethylcyclohexyl) -2,3-difluoro-4- (1-p-tolylalloxy) -5-vinylbenzene

In analogy to the synthesis described in Example 1 is obtained by Wittig reaction of 5- (4-trans-ethyl-cyclohexyl) -3,4-difluoro-2- (1 -p-tolyl-allyloxy) benzaldehyde with methylenetriphenyl-λ ^5- phosphane, the 1- (4-trans-ethyl-cyclohexyl) -2,3-difluoro-4- (1 -p-tolyl-allyloxy) -5-vinyl-benzene in 83 percent. Yield as a colorless solid.

3rd stage: 6- (4-trans-ethylcyclohexyl) -7,8-difluoro-2-p-tolyl-2H-chromen

In analogy to the synthesis described in Example 1, ring-closing metathesis of 1- (4-trans-ethyl-cyclohexyl) -2,3-difluoro-4- (1-p-tolyl-allyloxy) -5-vinyl-benzene affords 6 - (4-trans-ethyl-cyclohexyl) -7,8-difluoro-2-p-tolyl-2H-chromene in 69 percent. Yield as colorless crystals.

4th step: 6- (4-trans-ethylcyclohexyl) -7,8-difluoro-2-p-tolylchroman

6- (4-trans-ethyl-cyclohexyl) -7,8-difluoro-2-p-tolyl-2H-chromen is hydrogenated analogously to the synthesis described in Example 1. This gives 6- (4-trans-ethyl-cyclohexyl) -7,8-difluoro-2-p-tolyl-chroman in 92 percent. Yield as colorless crystals. Δε = - 4.1

Δn = 0.1561

Example 6 Trans 3- (4-ethylcyclohexyl) oxetane

The compound of the following formula

is made as follows:

67.4 ml of BuLi (15% in hexane) are added dropwise at 0 ° C. to a solution of 20 g of diol (11) in 100 ml of THF. After 30 minutes, a solution of 19 g of tosyl chloride in 100 ml of THF is added dropwise (exothermic, heating to about 40 ° C) and the resulting mixture stirred for 1 hour at room temperature before further 67.4 ml BuLi are added with ice cooling. The reaction is heated at 60 [deg.] C. for 4 hours. The THF is on the

Rotary evaporator removed, the residue treated with water and MTBE, the organic phase separated, dried and concentrated by rotary evaporation. Purification of the residue by column chromatography (heptane / EA 6: 1) gives 11.1 g of a colorless oil (12). Yield: 61% Analogously to Example 6, the following compounds of Examples 7 and 8 are obtained using the corresponding precursors:

Example 7 Trans 3- (4-n-propylcyclohexyl) oxetane

Yield: 68%

Example 8 trans 3- (4 ^' - n -propyl-bicyclohexyl-4-yl) -oxetane

Yield: 57%

Example 9 (Ortho-lithiation) Trans-2- (4-ethyl-cyclohexyl) -3- (2,3,4-trifluoro-phenyl) -propan-1-ol

The compound of the following formula

is made as follows:

To a solution of 8.7 g of trifluorobenzene in 100 ml of THF under nitrogen at -78 ° C 40 ml of BuLi (15% in hexane) was slowly added dropwise and stirred at this temperature for 1 hour. The deep yellow solution is first injected with 7.6 g of the indicated oxetane (HPLC content 90% trans, 10% ice) and, after 15 minutes, 5.1 ml of BF ₃ etherate dropwise. When adding the BF ₃ -Etherats must be well cooled to keep the Reaktions¬ temperature below -7O ° C. After 60 minutes of stirring at -8O ° C (TLC control, complete conversion) is quenched with 50 ml of ammonium chloride solution at -78 ° C. The thawed reaction mixture is mixed with MTBE, slightly acidified with 2N HCl, the aqueous phase is separated off and repeatedly extracted with MTBE. The combined organic phases are washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated by rotary evaporation. Purification of the residue by chromatography over 500 ml of silica gel (eluent: toluene) gives 10.7 g of a colorless oil. By HPLC, the content of the desired trans compound is 81%.

Yield: 71%.

Analogously to Example 9, the following compounds of Examples 10 to 17 are obtained using the corresponding oxetane precursors. If the lithiated aromatic is prepared by halogen-metal exchange, the solvent used is diethyl ether.

Example 18 (Cyclization) trans-7,8-Difluoro-3- (4- (ethyl) -cyclohexyl) -chroman

The compound of the following formula

is made as follows:

A solution of 10 g of the alcohol (content 95%) in 250 ml of THF is slowly added dropwise to a suspension of 4.6 g of KH (30% in paraffin oil) in 500 ml of THF under N ₂ at 40 ° C. After a further 2 hours at 55 ° C, the reaction is complete according to TLC control. It is quenched with 10 ml of saturated ammonium chloride solution, the majority of the THF is removed, toluene is added, the mixture is extracted with water and the organic phase is separated off. The aqueous phase is back-extracted three times with toluene. The combined organic phases are dried over sodium sulfate, concentrated by rotary evaporation and the residue is purified by column chromatography (heptane / toluene 19: 1). This gives 6.8 g of a colorless solid.

Yield: 76%

By recrystallization, the pure trans compound is obtained: K 82 I Δn: 0.0729 Δε: 11, 8 KIp .: -9.1 ° C.

Analogously, using the corresponding precursors, the following compounds of Examples 19 to 25 are obtained:

Example 26

Under nitrogen, 1.01 g of 3,4,5-trifluorophenylboronic acid (1.1 equivalents), 2.00 g of 6-fluoro-3- (4-propyl-cyclohexyl) -7-bromo-chroman (1, 0 equiv .), 1, 3 g of sodium metaborate octahydrate (0.84 equiv.) And 141 mg of bis (triphenylphosphine) palladium (II) chloride (3.5 mol%) were suspended in 20 ml of THF and 5 ml of water. The mixture is heated while stirring vigorously

75 ° C until the bromine-chroman is completely reacted (3 to 12 hours). After cooling, the aqueous phase is separated and back-extracted three times with MTBE. The combined organic phases are washed with sodium chloride solution, dried and concentrated by rotary evaporation. The crude product is purified by column chromatography over silica gel with heptane / toluene (6: 1) as eluent.

This gives 2.05 g of product with a content of 91%, corresponding to a yield of 82%. Recrystallization from heptane / iso-propanol gives 1.4 g of product with a content of> 99.5%.

K 102 N 115.1 I Δn: 0.1397 Δε: 24.7 KIp .: 88.5 ° CY ₁ : 996 mPas Analogously to Example 26, the following compounds of Examples 27 to 31 are obtained using the corresponding precursors:

Example 27

Yield: 68%

K 101 N (81, 9) Δn: 0.1305 Δε: 27.4 Clp .: 76.3 ° C

Example 28

Yield: 86%

K 100 N 180.1 Δn: 0.1442 Δε: 35.1 clp .: 165.7 ° C γi: 1261 mPas Example 29

Yield: 72%

K 106 N 166.6 Δn: 0.1320 Δε: 36.2 clp .: 155.4 ° C

Example 30

Yield: 88%

K 95 SmA 141 N 190 Δn: 0.1388 Δε: 35.8 KIp .: 177.6 ° C Example 31

Yield: 71%

K 109 N 161, 5 Δn: 0.1404 Δε: 34.8 KIp .: 132, O ° C

Analogously to Examples 1 to 5, the following compounds of Examples 32 to 2506 are obtained using the corresponding precursors:

Examples 32 - 106

Examples 107-181

Examples 182-256

Examples 257-331

Examples 332-406

Examples 407-481

Examples 482-556

Examples 557-631

Examples 632-706

Examples 707-781

Examples 782-856

Examples 857-931

Examples 932-1006

Examples 1007-1081

Examples 1082-1 156

Examples 1157-1231

Examples 1232-1306

Examples 1307-1381

Examples 1382-1456

Examples 1457-1531

Examples 1532-1606

Examples 1607-1681

Examples 1682-1756

Examples 1757-1831

Examples 1832-1906

Examples 1907-1981

Examples 1982-2056

Examples 2057-2131

Examples 2132-2206

Examples 2207-2281

Examples 2282-2356

Examples 2357-2431

Examples 2432-2506

Analogously to Examples 6 to 31, the following compounds of Examples 2507 to 4306 are obtained using the corresponding precursors:

Examples 2507 to 2551

Examples 2552 to 2596

Examples 2597 to 2641

Examples 2642 to 2686

58

-115-

Examples 2687 to 2731

Examples 2732 to 2776

Examples 2777 to 2821

Examples 2822 to 2866

Examples 2867 to 291 1

Examples 2912 to 2956

Examples 2957 to 3001

Examples 3002 to 3046

Examples 3047 to 3091

Examples 3092 to 3136

Examples 3137 to 3181

Examples 3182 to 3226

Examples 3227 to 3271

Examples 3272 to 3316

Examples 3317 to 3361

Examples 3362 to 3406

Examples 3407 to 3451

Examples 3452 to 3496

Examples 3497-3541

Examples 3542 to 3586

Examples 3587 to 3631

Examples 3632 to 3676

Examples 3677 to 3721

Examples 3722 to 3766

Examples 3767 to 3811

Examples 3812 to 3856

Examples 3857 to 3901

Examples 3902 to 3946

Examples 3947 to 3991

Examples 3992 to 4036

Examples 4037 to 4081

Examples 4082 to 4126

Examples 4127 to 4171

Examples 4172 to 4216

Examples 4217 to 4261

Examples 4262 to 4306

Example 4307 7,8-Difluoro-6- (4-pentylcyclohexyl) -2-propyichroman

1st stage: 7,8-Difluoro-6- (4-penty! Cyclohexyl) -2-propyl-2H-chromene

After Q. Wang, NG Finn, Org. Lett. 2000, pp 4063-4065, 5 g (16.1 mmol) of 3,4-difluoro-2-hydroxy-5- (4-pentylcyclohexyl) benzaldehyde and 3.8 g (33.3 mmol) of E-pent 1-enylboronic acid in the presence of 0.6 ml of dibenzylamine in 80 ml of dioxane for 48 hours at 90 ° C left to stir. After addition of water, it is extracted with MTB ether and the combined organic phases are concentrated. The residue is chromatographed on silica gel with heptane / chlorobutane (10: 1). This gives 5.8 g (86%) of 7,8-difluoro-6- (4-pentyl-cyclohexyl) -2-propyl-2H-chromene as a colorless oil. 2nd Step: 7,8-Difluoro-6- (4-pentylcyclohexyl) -2-propylchroman

4.8 g (13.1 mmol) of 7,8-difluoro-6- (4-pentylcyclohexyl) -2-propyl-2H-chromene are dissolved in 50 ml of THF and hydrogenated to standstill in the presence of palladium activated carbon catalyst , The solution is filtered, the solvent removed in vacuo and the residue recrystallized from ethanol. 3.4 g (71%) of 2-ethyl-6- (4-ethylcyclohexyl) -7,8-difluorochromane are obtained as colorless crystals.

T ₉ -53 K 55 N (15.3) I Δε = -7.3 Δn = 0.0812

Analogously to Example 4307, the following compounds of Examples 4308 to 4333 are obtained using the corresponding precursors.

Example 4308 7,8-Difluoro-2-pentyl-6- (4-pentyl-cyclohexyl) -chroman

K 34 N (25.2) Δε = -6.8 Δn = 0.0746 Example 4309 7,8-Difluoro-2- (4-pentyl-cyclohexyl) -6- (4'-propyl-bicyclohexyl-4-yl) -chroman

K 143 SmA (139) N 277.5 I Δε = -5.4

Δn = 0.0712

Example 4310 7,8-Difluoro-6- (4-pentyl-phenyl) -2-propyl-chroman

K 51 I Δε = -7.0 Δn = 0.1407

Example 4311 7,8-Difluoro-2-methyl-6- (4-butyl-cyclohexyl) -chroman

K 75 I Δε = -6.8 Δn = 0.0797 Example 4312 7,8-Difluoro-2-methyl-6- (4'-propyl-bicyclohexyl-4-yl) -chroman

K 150 N 157 I Δε = -6.7 Δn = 0.0758

Example 4313 2- (4-butylcyclohexyl) -6-ethoxy-7,8-difluoro-chroman

K 100 I Δε = -10.8 Δn = 0.0834

Example 4314 6-Ethoxy-7,8-difluoro-2- (4'-propyl-bicyclohexyl-4-yl) -chroman

K 155 N 187 I Δn = 0.0766 For example 4315

K 119 I

Example 4316

K 81 SmA (75) N 177 Δε = 31, 3 Δn = 0.1430

Example 4317

K 110 N 145.7 Δε = 36.9 Δn = 0.1358 Example 4318

K 102 I Δ∈ = 42.3 Δn = 0.1354

Example 4319

K 99 SmA 126 N 174 Δε = 41, 6 Δn = 0.1366

Example 4320

K 89 SmA 150 N 186.6 l

Δε = 34.3 Δn = 0.1351 Example 4321

K 98 SmA 110 N 157.8 I Δε = 37.9 Δn = 0.1295

Example 4322

K 88 SmA 124 N 176.8 I Δε = 39.1 Δn = 0.1317

Example 4323

K 121 I Example 4324

K 122 N 152.3 I Δε = 46.0 Δn = 0.1406

Example 4325

K 107 SmA (83) N 169.4 Δε = 44.2 Δn = 0.1404

Example 4326

K 83 SmA 104 N 167.7 I

Δε = 42.6 Δn = 0.1392 Example 4327

K 134 N 180.7 I Δ∈ = 32.3 Δn = 0.1498

Example 4328

K 110 N 197.8 I Δε = 32.5 Δn = 0.1535

Example 4329

K 106 SmA (104) N 193.8 I Δε = 30.3 Δn = 0.1501 Example 4330

K 145 N 204.1 I Δn = 0.1623

Example 4331

K 142 N 215.2 Δn = 0.1559

Example 4332

K 132 N 208.9 l

Example 4333

K 104 N 190.7 I

Example 4334

A liquid crystal mixture containing

BCH-3F.F 10.80%

BCH-5F.F 9.00% ECCP-3OCF3 4.50%

ECCP-5OCF3 4.50%

CBC-33F 1, 80%

CBC-53F 1, 80%

CBC-55F 1, 80% PCH-6F 7.20%

PCH-7F 5.40%

CCP-2OCF3 7.20%

CCP-3OCF3 10.80%

CCP-4OCF3 6.30% CCP-5OCF3 9.90%

PCH-5F 9.00%

Connection of Example 26 10.00%

has the following properties: clearing point: + 92.3 ° C Δε: +7.3

Δn: +0.1012

Example 4335

A liquid crystal mixture containing

BCH-3F.F 10.80% BCH-5F.F 9.00%

ECCP-3OCF3 4.50% ECCP-5OCF3 4.50%

CBC-33F 1, 80%

CBC-53F 1, 80%

CBC-55F 1, 80%

PCH-6F 7.20%

PCH-7F 5.40%

CCP-2OCF3 7.20%

CCP-3OCF3 10.80%

CCP-4OCF3 6.30%

CCP-5OCF3 9.90%

PCH-5F 9.00%

Connection of Example 28 10.00%

has the following properties: clearing point: +97.1 ° C Δε: +8.4

Δn: +0.1028

Example 4336

Containing a liquid crystal mixture

BCH-3F.F 10.80% BCH-5F.F 9.00%

ECCP-3OCF3 4.50%

ECCP-5OCF3 4.50%

CBC-33F 1, 80%

CBC-53F 1, 80% CBC-55F 1, 80%

PCH-6F 7.20%

PCH-7F 5.40%

CCP-2OCF3 7.20%

CCP-3OCF3 10.80% CCP-4OCF3 6.30%

CCP-5OCF3 9.90% PCH-5F 9.00%

Connection of Example 18 10.00%

has the following properties: clearing point: + 80.7 ° C Δε: +5.8

Δn: +0.0916

Example 4337

A liquid crystal mixture containing

PCH-301 9.00%

PCH-302 9.00%

CCH-301 29.70%

CCN-47 9.90%

CCN-55 9.00%

CBC-33F 4.50%

CBC-53F 4.50%

CBC-55F 4.50%

CBC-33 4.50%

CBC-53 5.40%

Connection of Example 18 10.00%

has the following properties: clearing point: + 72.0 ° C Δε: -0.4

Claims

claims

1. Chroman derivatives of the general formula (I)

wherein

R ¹ H, halogen (F, Cl, Br, I), a linear or branched, optionally chiral, unsubstituted, one simply by CN or CF ₃ or at least one by

Halogen-substituted alkyl radical having 1 to 15 C atoms or alkenyl radical having 2 to 15 C atoms, in which one or more CH ₂ groups are each independently denoted by -O-, -S-, -CO-, -CO-O- , -O-CO-, -O-CO-O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C- or -ζ) - such may be replaced, that heteroatoms are not directly linked,

R ^{2 is} H, F, Cl, NCS, CN, SF ₅ , an alkyl or alkoxy radical having 1 to

15 C atoms, an alkenyl or Alkenyloxyrest with 2 to 15 C-atoms, a substituted by one or more fluorine atoms alkyl or alkoxy radical having 1 to 15 carbon atoms or substituted by one or more fluorine atoms alkenyl or Alkenyloxyrest with 2 up to 15 C atoms,

A ¹ , A ^{2 are} each independently, the same or different

a) trans-1,4-cyclohexylene, in which also one or more non-adjacent CH ₂ groups can be replaced by -O- and / or -S-, b) 1,4-phenylene, in which one or two CH groups may be replaced by N and in which also one or more H atoms may be replaced by F,

c) a radical from the group 1, 4-bicyclo (2,2,2) -octylene, piperidine-1, 4-diyl, naphthalene-2,6-diyi, decahydronaphthalene-2,6-diyl and 1, 2, 3,4-tetrahydronaphthalene-2,6-diyl, or

d) 1,4-cyclohexenylene,

Each of Z ¹ , Z ² is independently, identically or differently -O-, -CH ₂ O-, -OCH ₂ -, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ O-, -OCF ₂ CH ₂ -, -CH ₂ CH ₂ -,

-CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CF = CF-CO-O-, -O-CO-CF = CF-, -C≡C- or a single bond,

L ¹ , L ² , L ^{3 are} each independently, identically or differently H, F, Cl, NCS, CN, SF ₅ or a substituted by one or more fluorine atoms alkyl or alkoxy radical having 1 to 15 C atoms, a by one or more fluorine atoms substituted alkenyl or alkenyloxy having 2 to 15 C atoms, preferably H, F, Cl or CN, and particularly preferably H or F,

m is O, 1, 2, 3 or 4, preferably 0, 1, 2 or 3 and more preferably O, 1 or 2, and

n is 1, 2, 3 or 4, preferably 1, 2 or 3 and more preferably 1 or 2,

but with the proviso that the sum (m + n) = 1, 2, 3 or 4, preferably 1, 2 or 3 and more preferably 1 or 2,

and the general formula (II)

L ¹ , L ² , L ³ and L ^{4 are} each independently, identically or differently H, F, Cl, NCS, CN, SF ₅ or a substituted by one or more fluorine atoms alkyl or alkoxy radical having 1 to 15 carbon atoms, a substituted by one or more fluorine atoms alkenyl or Alkenyloxyrest having 2 to 15 carbon atoms, preferably H, F, Cl or CN, and particularly preferably H or F, wherein

L ² and L ³ together too

L ⁵ and L ⁶ each independently, identically or differently H, F, Cl or CN and one of the two radicals additionally also - (Z ² -A ² -) _n R ² , mean

but with the proviso that when L ⁵ and L ^{6 are} each independently, identically or differently H, F, Cl or CN, m = 1, 2, 3 or 4, preferably 1, 2 or 3 and most preferably 1 or 2 . and when one of the two radicals is - (Z ² -A ² -) _n R ² , m and n are each, independently or differently, 0, 1, 2, 3 or 4, the sum (m + n ) = 1, 2, 3 or 4, preferably 1, 2 or 3,

and chromene derivatives of the general formulas (III) and (IV)

and chromene derivatives of the general formulas (V) and (VI)

2. Chroman derivatives according to claim 1, characterized in that the compounds of sub-formula (I) are compounds of the following sub-formulas:

wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² , L ³ , m and n have the meanings given in relation to formula (I) in claim 1. 10458

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3. Chroman derivatives according to claim 2, characterized in that the compounds of sub-formula (Ia) are compounds of the following sub-formulas:

wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (I) in claim 1.

4. Chroman derivatives according to claim 2, characterized in that the compounds of sub-formula (Ib) are compounds of the following sub-formulas:

5. Chroman derivatives according to claim 1, characterized in that the compounds of sub-formula (II) are compounds of the following sub-formulas:

wherein R ¹ , A ¹ , Σ \ L ¹ , L ² , L ³ , L ⁴ and m have the meanings given in relation to formula (I) and R ² with respect to formula (I) in claim 1.

6. Chroman derivatives according to claim 5, characterized in that the compounds of sub-formula (IIa) are compounds of the following sub-formulas:

wherein R ¹ , A ¹ , Z ¹ , L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (I) and R ² with respect to formula (I) in claim 1.

7. chroman derivatives of the general formulas (Mal) to (Ila3) according to Claim 6, characterized in that they have the following structures:

wherein R ¹ , A ¹ and Z ¹ assume the meanings given in relation to formula (II) in claim 1, R ² assumes the meanings given in relation to formula (I) in claim 1 and m = 1, 2 or 3.

8. Chroman derivatives according to claim 5, characterized in that the compounds of sub-formula (IIb) are compounds of the following sub-formulas:

wherein R ¹ , A ¹ , Z \ L ¹ , L ² and L ^{3 have} the meanings given in relation to formula (I) and R ² with respect to formula (I) in claim 1.

9. chroman derivatives of the general formulas (UbI) to (IIb3) according to claim 8, characterized in that they have the following structures:

(C9)

10. chroman derivatives of the formula (II) according to at least one of claims 5 to 9, characterized in that the compounds of the formula (II) are compounds having a ring in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - the subformulae a and b

R ¹ -A ² - a R ¹ -A ² -Z ² - b

is.

11. Chroman derivatives of the formula (II) according to at least one of claims 5 to 9, characterized in that the compounds of the formula (II) are compounds with two rings in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - the sub-formulas c to f R ¹ -AA ² - c

R ¹ -A ¹ -A ² -Z ² - d

R ¹ -A ¹ -Z ¹ -A ² - e

R ¹ -A ¹ -Z ¹ -A ² -Z ² - f

is.

12. chroman derivatives of the formula (II) according to at least one of claims 5 to 9, characterized in that it is in the

Compounds of the formula (II) to compounds having three rings in the mesogenic group R ¹ (-A ¹ -Z ¹ ) _m - of the partial formulas g to o

R ¹ -A ¹ -A ¹ -A ² - g

R ¹ -A ¹ -Z ¹ -A ¹ -A ² - h

R ¹ -A ¹ -A ¹ -Z ¹ -A ² - i

R ¹ -A ¹ -A ¹ -A ² -Z ² - j

R ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ -A ² - k

R ¹ -A ¹ -Z ¹ -A ¹ -A ² -Z ² - m

R ¹ -A ¹ -A ¹ -Z ¹ -A ² -Z ² - n

R ¹ -A ¹ -Z ¹ -A ¹ -Z ¹ -A ² -Z ² - o

is.

13. Chroman derivatives according to claim 10, characterized in that the compounds of sub-formula a are compounds of the following sub-formulas

is.

14. Chroman derivatives according to claim 11, characterized in that the compounds of sub-formula c are compounds of the following sub-formulas

is.

15. chroman derivatives according to claim 1 1, characterized in that it is in the compounds of the partial formula d compounds of the following sub-formulas

is.

16. chroman derivatives according to claim 11, characterized in that it is the compounds of the sub-formula e compounds of the following sub-formulas

is.

17. Use of chroman derivatives of the formulas (I) and (II) and chromene derivatives of the formulas (III) to (VI) according to at least one of the preceding claims as component (s) in liquid-crystalline media.

18. Liquid-crystalline medium having at least two liquid-crystalline components, characterized in that it contains at least one chroman and / or chromene derivative of the formulas (I) to (VI) according to at least one of claims 1 to 16.

19. Liquid crystal display element, characterized in that it contains a liquid-crystalline medium according to claim 18.

20. An electro-optical display element, characterized in that it contains a liquid-crystalline medium according to claim 18 as a dielectric.