DE19807371A1 - New perfluoroalkyltetrafluorosulfanyl derivatives of cyclic ethyne or ethene compounds used as components of liquid crystal media - Google Patents

Abstract

Perfluoroalkyltetrafluorosulfanyl derivatives of cyclic ethyne or ethene compounds (I) are new and have high thermal stability. Perfluoroalkyltetrafluorosulfanyl derivatives of cyclic ethyne or ethene compounds of formula (I) are new. R<1> = H, 1-12C alkyl or 2-12C alkenyl, which may be mono-substituted by CN or CF3 or at least mono-substituted by halogen and in which one or more non-adjacent -CH2- groups may be replaced by O, S, CO, 1,3-cyclobutylene, COO, OCO or OCOO; A<1>, A = (a) trans-cyclohexan-1,4-diyl, in which one or more non-adjacent CH2 groups may be replaced by O and/or S, (b) 1,4-phenylene, in which one or 2 CH groups may be replaced by N, (c) 1,4-bicyclo(2,2,2)-octylene, piperidin-1,4-diyl, naphthalen-2,6-diyl, decahydronaphthalen-2,6-diyl and 1,2,3,4-tetrahydronaphthalen-2,6-diyl, (d) cyclohexen-1,4-diyl and groups (a), (b) and (d) may be substituted by CN, Cl or F; Q = -C equivalent to C- or -CX<1>=CX<2>-; X<1>, X<2> = H or F; Z = -COO-, -OCO-, -CH2O-, O, -OCH2-, -CH2CH2-, -CH=CH-, -C equivalent to C-, a single bond or a group of formula -(CF=CF)u- or (CF2)v; u, n = 1, 2 or 3; v = 2, 3 or 4; and m = 1-10.

Description

The invention relates to new perfluoroalkltetrafluorosulfanyl derivatives of the formula I.

R ¹ - (A ¹ -Z) _n -AQ-SF ₄ C _m F _{2m + 1} I

wherein
R ¹ H, an unsubstituted, a simply by CN or CF ₃ or an at least mono-substituted alkyl radical with 1-12 carbon atoms or alkenyl radical with 2-12 carbon atoms, in which radicals one or more non-adjacent CH ₂ groups can each be replaced independently of one another by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O,
A ¹ , A one

• a) trans-cyclohexane-1,4-diyl radical, in which one or more non-adjacent CH ₂ groups can also be replaced by -O- and / or -S-,
• b) 1,4-phenylene radical, in which also one or two CH groups can be replaced by N,
• c) residue from the group 1,4-bicyclo (2,2,2) octylene, pipe ridin-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene 2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
• d) cyclohexene-1,4-diyl

where the radicals a), b) and d) can be substituted by CN, Cl or F,

X ¹ , X ² each independently of one another H or F,
Z -CO-O-, -O-CO-, -CH ₂ O-, -O-, -O-CH ₂ , -CH ₂ CH ₂ -, -CH = CH-, -C∼C-, a single bond ,

u 1, 2 or 3
v 2, 3 or 4
n 1, 2 or 3
and
m 1 to 10
means.

The invention further relates to the use of these compounds as Components of liquid crystalline media as well as liquid crystal and electro optical display elements, the liquid crystalline according to the invention Media included.

The compounds of the formula I can be liquid-crystalline as components Media are used, especially for displays based on the principle the twisted cell, the guest-host effect, the effect of the deformation erected phases DAP or ECB, Electrically controlled birefringence or based on the effect of dynamic scattering. So far for this  Purpose-used substances always have certain disadvantages, for example show insufficient stability against the effects of heat, light or electrical fields, unfavorable elastic and / or dielectric Characteristics.

The invention was based on the object, new stable liquid-crystalline or find mesogenic compounds as components liquid crystalline media, especially for TFT and STN displays, are suitable.

It has now been found that the compounds of the formula I are excellent as Components of liquid crystalline media are suitable. With her help read stable liquid-crystalline media, particularly suitable for TFT or STN displays. The new connections are emerging all characterized by a high thermal stability, which holds for a high " ratio "is advantageous and show at comparatively low rotation viscosity favorable values of the clearing points. The compounds of formula I. exhibit a comparatively strong positive dielectric anisotropy low optical anisotropy at the same time.

With the provision of compounds of formula I becomes very general the range of liquid crystalline substances, which can be found under different application aspects for the production of liquid crystal liner mixtures are suitable, considerably widened.

The compounds of formula I have a wide range of uses Area. Depending on the selection of the substituents, these can Compounds serve as base materials from which liquid crystalline The majority of the media are composed; but it can also compounds of formula I liquid crystalline base materials other classes of compounds, for example the dielectric and / or optical anisotropy of such a dielectric influence and / or around its threshold voltage and / or its Optimize viscosity. From Formula I all isotopes of the in the compounds of formula I occurring elements.  

The compounds of the formula I are colorless in the pure state and form liquid crystalline mesophases in one for electro-optical use conveniently located temperature range. Chemical, thermal and against Light they are stable.

The invention thus relates to the compounds of the formula I and the use of these compounds as components of liquid crystalline Media. The invention also relates to liquid-crystalline media containing at least one compound of formula I and liquid crystal display elements, in particular electro-optical display elements, that contain such media.

Above and below, R ¹ , Q, A, A ¹ , Z, L ¹ , L ² , L ³ , m, n, u and v have the meaning given, unless expressly stated otherwise.

For the sake of simplicity, Cyc in the following means a 1,4-cyclo hexylene radical, Che a 1,4-cyclohexenylene radical, dio a 1,3-dioxane-2,5- diyl residue, Dit a 1,3-dithiane-2,5-diyl residue, Phe a 1,4-phenylene residue, Pyd a pyridine-2,5-diyl radical, Pyr a pyrimidine-2,5-diyl radical and Bco one Bicyclo (2,2,2) octylene radical, where Cyc and / or Phe is unsubstituted or can be substituted one or more times by Cl, F or CN.

Formula I comprises the preferred compounds Ia1 to Ia7 which contain two six-membered rings:

R ¹ -A ¹ -AQ-SF ₄ C _m F _{2m + 1} Ia1
R ¹ -A ¹ -CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ia2
R ¹ -A ¹ -CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ia3
R ¹ -A ¹ -CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ia4
R ¹ -A ¹ -COO-AQ-SF ₄ C _m F _{2m + 1} Ia5
R ¹ -A ¹ -OOC-AQ-SF ₄ C _m F _{2m + 1} Ia6
R ¹ -A ¹ -C∼CAQ-SF ₄ C _m F _{2m + 1} Ia7.

Furthermore, the preferred compounds Ib1 to Ib41, which contain three six-membered rings:

R ¹ -A ¹ -Phe-AQ-SF ₄ C _m F _{2m + 1} Ia1
R ¹ -A ¹ -CH ₂ CH ₂ -Phe-AQ-SF ₄ C _m F _{2m + 1} Ib1
R ¹ -A ¹ -CH = CH-Phe-AQ-SF ₄ C _m F _{2m + 1} Ib2
R ¹ -A ¹ -CF = CF-Phe-AQ-SF ₄ C _m F _{2m + 1} Ib3
R ¹ -A ¹ -COO-Phe-AQ-SF ₄ C _m F _{2m + 1} Ib4
R ¹ -A ¹ -C∼C-Phe-AQ-SF ₄ C _m F _{2m + 1} Ib5
R ¹ -A ¹ -Pyr-AQ-SF ₄ C _m F _{2m + 1} Ia1
R ¹ -A ¹ -CH ₂ CH ₂ -Pyr-AQ-SF ₄ C _m F _{2m + 1} Ib1
R ¹ -A ¹ -CH = CH-Pyr-AQ-SF ₄ C _m F _{2m + 1} Ib2
R ¹ -A ¹ -CF = CF-Pyr-AQ-SF ₄ C _m F _{2m + 1} Ib3
R ¹ -A ¹ -COO-Pyd-AQ-SF ₄ C _m F _{2m + 1} Ib4
R ¹ -A ¹ -C∼C-Pyd-AQ-SF ₄ C _m F _{2m + 1} Ib5
R ¹ -A ¹ -Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib6
R ¹ -A ¹ -CH ₂ CH ₂ -Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib7
R ¹ -A ¹ -CH = CH-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib8
R ¹ -A ¹ -CF = CF-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib9
R ¹ -A ¹ -COO-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib10
R ¹ -A ¹ -OOC-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib11
R ¹ -A ¹ -C∼C-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ib12
R ¹ -A ¹ -Dio-AQ-SF ₄ C _m F _{2m + 1} Ib13
R ¹ -A ¹ -CH ₂ CH ₂ -dio-AQ-SF ₄ C _m F _{2m + 1} Ib14
R ¹ -A ¹ -CH = CH-Dio-AQ-SF ₄ C _m F _{2m + 1} Ib15
R ¹ -A ¹ -CF = CF-Dio-AQ-SF ₄ C _m F _{2m + 1} Ib16
R ¹ -A ¹ -COO-Dio-AQ-SF ₄ C _m F _{2m + 1} Ib17
R ¹ -A ¹ -OOC-Dio-AQ-SF ₄ C _m F _{2m + 1} Ib18
R ¹ -A ¹ -C∼C-Dio-AQ-SF ₄ C _m F _{2m + 1} Ib19
R ¹ -A ¹ -Phe-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ib20
R ¹ -A ¹ -Pyr-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ib21
R ¹ -A ¹ -Cyc-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ib22
R ¹ -A ¹ -dio-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ib23
R ¹ -A ¹ -Phe-CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ib24
R ¹ -A ¹ -Pyr-CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ib25
R ¹ -A ¹ -Cyc-CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ib26
R ¹ -A ¹ -dio-CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ib27
R ¹ -A ¹ -Phe-CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ib28
R ¹ -A ¹ -Pyd-CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ib29
R ¹ -A ¹ -Cyc-CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ib30
R ¹ -A ¹ -Dio-CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ib31
R ¹ -A ¹ -Cyc-COO-AQ-SF ₄ C _m F _{2m + 1} Ib32
R ¹ -A ¹ -dio-COO-AQ-SF ₄ C _m F _{2m + 1} Ib33
R ¹ -A ¹ -Phe-OOC-AQ-SF ₄ C _m F _{2m + 1} Ib34
R ¹ -A ¹ -Pyr-OOC-AQ-SF ₄ C _m F _{2m + 1} Ib35
R ¹ -A ¹ -Cyc-OOC-AQ-SF ₄ C _m F _{2m + 1} Ib36
R ¹ -A ¹ -Dio-OOC-AQ-SF ₄ C _m F _{2m + 1} Ib37
R ¹ -A ¹ -Phe-C = CAQ-SF ₄ C _m F _{2m + 1} Ib38
R ¹ -A ¹ -Pyd-C∼CAQ-SF ₄ C _m F _{2m + 1} Ib39
R ¹ -A ¹ -Cyc-C∼CAQ-SF ₄ C _m F _{2m + 1} Ib40
R ¹ -A ¹ -Dio-C∼CAQ-SF ₄ C _m F _{2m + 1} Ib41.

Formula I further comprises the following preferred compounds Ic1 to Ic90 with four six-membered rings:

R ¹ -A ¹ -Phe-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic1
R ¹ -A ¹ -CH ₂ CH ₂ -Phe-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic2
R ¹ -A ¹ -COO-Phe-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic3
R ¹ -A ¹ -Cyc-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic4
R ¹ -A ¹ -CH ₂ CH ₂ -Cyc-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic5
R ¹ -A ¹ -OOC-Cyc-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic6
R ¹ -A ¹ -dio-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic7
R ¹ -A ¹ -CH ₂ CH ₂ -dio-Pyd-ZAQ-SF ₄ C _m F _{2m + 1} Ic8
R ¹ -A ¹ -OOC-Dio-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic9
R ¹ -A ¹ -dio-CH = CH-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic10
R ¹ -A ¹ -Phe-CF = CF-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic11
R ¹ -A ¹ -Cyc-COO-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic12
R ¹ -A ¹ -dio-COO-Pyr-ZAQ-SF ₄ C _m F _{2m + 1} Ic13
R ¹ -A ¹ -Phe-C = C-Phe-ZAQ-SF ₄ C _m F _{2m + 1} Ic14
R ¹ -A ¹ -Cyc-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic15
R ¹ -A ¹ -CH ₂ CH ₂ -Cyc-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic16
R ¹ -A ¹ -COO-Cyc-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic17
R ¹ -A ¹ -OOC-Cyc-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic18
R ¹ -A ¹ -dio-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic19
R ¹ -A ¹ -CH ₂ CH ₂ -dio-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic20
R ¹ -A ¹ -OOC-Dio-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic21
R ¹ -A ¹ -Cyc-CH ₂ CH ₂ -Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic22
R ¹ -A ¹ -dio-CH ₂ CH ₂ -Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic23
R ¹ -A ¹ -Cyc-CH = CH-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic24
R ¹ -A ¹ -Dio-CF = CF-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic25
R ¹ -A ¹ -Cyc-COO-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic26
R ¹ -A ¹ -dio-COO-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic27
R ¹ -A ¹ -Cyc-OOC-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic28
R ¹ -A ¹ -Cyc-C∼C-Cyc-ZAQ-SF ₄ C _m F _{2m + 1} Ic29
R ¹ -A ¹ -Cyc-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic30
R ¹ -A ¹ -CH ₂ CH ₂ -Cyc-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic31
R ¹ -A ¹ -CF = CF-Cyc-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic32
R ¹ -A ¹ -COO-Cyc-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic33
R ¹ -A ¹ -OOC-Cyc-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic34
R ¹ -A ¹ -dio-dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic35
R ¹ -A ¹ -CH ₂ CH ₂ -dio-dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic36
R ¹ -A ¹ -CH = CH-Dio-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic37
R ¹ -A ¹ -CF = CF-Dio-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic38
R ¹ -A ¹ -COO-Dio-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic39
R ¹ -A ¹ -dio-CH ₂ CH ₂ -dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic40
R ¹ -A ¹ -Cyc-CH = CH-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic41
R ¹ -A ¹ -Cyc-CF = CF-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic42
R ¹ -A ¹ -Cyc-COO-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic43
R ¹ -A ¹ -Cyc-OOC-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic44
R ¹ -A ¹ -Dio-OOC-Dio-ZAQ-SF ₄ C _m F _{2m + 1} Ic45
R ¹ -A ¹ -Z-Pyd-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic46
R ¹ -A ¹ -Z-Phe-Phe-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic47
R ¹ -A ¹ -Z-Phe-Phe-COO-AQ-SF ₄ C _m F _{2m + 1} Ic48
R ¹ -A ¹ -Z-Cyc-Pyd-AQ-SF ₄ C _m F _{2m + 1} Ic49
R ¹ -A ¹ -Z-Cyc-Phe-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic50
R ¹ -A ¹ -Z-Cyc-Phe-OOC-AQ-SF ₄ C _m F _{2m + 1} Ic51
R ¹ -A ¹ -Z-Dio-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic52
R ¹ -A ¹ -Z-dio-pyr-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic53
R ¹ -A ¹ -Z-Dio-Phe-OOC-AQ-SF ₄ C _m F _{2m + 1} Ic54
R ¹ -A ¹ -Z-Dio-CH = CH-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic55
R ¹ -A ¹ -Z-Phe-CF = CF-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic56
R ¹ -A ¹ -Z-Cyc-COO-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic57
R ¹ -A ¹ -Z-Dio-COO-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic58
R ¹ -A ¹ -Z-Phe-C∼C-Phe-AQ-SF ₄ C _m F _{2m + 1} Ic59
R ¹ -A ¹ -Z-Cyc-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic60
R ¹ -A ¹ -Z-Cyc-Cyc-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic61
R ¹ -A ¹ -Z-Cyc-Cyc-COO-AQ-SF ₄ C _m F _{2m + 1} Ic62
R ¹ -A ¹ -Z-Cyc-Cyc-OOC-AQ-SF ₄ C _m F _{2m + 1} Ic63
R ¹ -A ¹ -Z-Dio-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic64
R ¹ -A ¹ -Z-Dio-Cyc-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic65
R ¹ -A ¹ -Z-Dio-Cyc-OOC-AQ-SF ₄ C _m F _{2m + 1} Ic66
R ¹ -A ¹ -Z-Cyc-CH ₂ CH ₂ -Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic67
R ¹ -A ¹ -Z-Dio-CH ₂ CH ₂ -Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic68
R ¹ -A ¹ -Z-Cyc-CH = CH-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic69
R ¹ -A ¹ -Z-Dio-CF = CF-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic70
R ¹ -A ¹ -Z-Cyc-COO-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic71
R ¹ -A ¹ -Z-Dio-COO-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic72
R ¹ -A ¹ -Z-Cyc-OOC-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic73
R ¹ -A ¹ -Z-Cyc-C∼C-Cyc-AQ-SF ₄ C _m F _{2m + 1} Ic74
R ¹ -A ¹ -Z-Cyc-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic75
R ¹ -A ¹ -Z-Cyc-Dio-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic76
R ¹ -A ¹ -Z-Cyc-Dio-CF = C FAQ-SF ₄ C _m F _{2m + 1} Ic77
R ¹ -A ¹ -Z-Cyc-Dio-COO-AQ-SF ₄ C _m F _{2m + 1} Ic78
R ¹ -A ¹ -Z-Cyc-Dio-OOC-AQ-SF ₄ C _m F _{2m + 1} Ic79
R ¹ -A ¹ -Z-Dio-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic80
R ¹ -A ¹ -Z-dio-dio-CH ₂ CH ₂ -AQ-SF ₄ C _m F _{2m + 1} Ic81
R ¹ -A ¹ -Z-dio-dio-CH = CH-AQ-SF ₄ C _m F _{2m + 1} Ic82
R ¹ -A ¹ -Z-Dio-Dio-CF = CF-AQ-SF ₄ C _m F _{2m + 1} Ic83
R ¹ -A ¹ -Z-dio-dio-COO-AQ-SF ₄ C _m F _{2m + 1} Ic84
R ¹ -A ¹ -Z-Dio-CH ₂ CH ₂ -Dio-AQ-SF ₄ C _m F _{2m + 1} Ic85
R ¹ -A ¹ -Z-Cyc-CH = CH-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic86
R ¹ -A ¹ -Z-Cyc-CF = CF-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic87
R ¹ -A ¹ -Z-Cyc-COO-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic88
R ¹ -A ¹ -Z-Cyc-OOC-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic89
R ¹ -A ¹ -Z-Dio-OOC-Dio-AQ-SF ₄ C _m F _{2m + 1} Ic90

wherein R ¹ , A ¹ , A, Q, m and Z have the meaning given above.

Q preferably means -C∼C-.

R ¹ preferably denotes straight-chain alkyl or alkoxy with 1 to 10 C atoms or alkenyl or alkenyloxy with 2 to 10 C atoms. The preferred meaning before n is 1 or 2.

X ¹ and X ^{2 are} preferably F or H, particularly preferably F.

A ¹ preferably denotes Phe, Cyc, Che, Pyd, Pyr or Dio, in particular Phe, Cyc or Dio. The compounds of the formula I preferably contain no more than one of the radicals Bco, Pyd, Pyr or Dit.

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

If the ring A ¹ is present more than once, the two rings can have the same or different meanings. The same also applies to the bridge Z and to all other groups which occur several times in the compounds of the formula I.

Also preferred are compounds of formula I and all sub-formulas in which A ¹ and / or A is 1,4-phenylene which is mono- or disubstituted by F or CN.

A ¹ and / or A preferably denotes:

Z preferably denotes -CH ₂ CH ₂ -, -CH = CH-, -C∼C-, -CF ₂ CF ₂ -, -CF = CF- or a single bond, particularly preferably a single bond, -CH ₂ -CH ₂ - or -CF ₂ CF ₂ -. Z very particularly preferably has the meaning of a single bond or -CF ₂ CF ₂ -.

Compounds of the formula I are preferred which are characterized in that R ¹ denotes straight-chain alkyl or alkoxy having 1 to 10 C atoms or alkenyl having 2 to 10 C atoms and Z is -CF ₂ CF ₂ - or -CF = CF- has.

Compounds of formula I, the group A

means put special embodiments of the invention.

Also particularly preferred are those compounds of the formula I which are characterized in that R ¹ denotes straight-chain alkyl or alkoxy having 1 to 10 C atoms or alkenyl or alkenyloxy having 2 to 10 C atoms and A is the meaning

having.  

In compounds of the formula I in which the group A or A ¹ denotes cyclohexane-1,4-diyl, the substituents in the 1- and 4-positions are in the trans position to one another.

m preferably denotes 1, 2, 3, 4, 5, 6, 7, 8 or 9. The by the parameter The characterized perfluoroalkyl group is preferably linear. she accordingly preferably means trifluoromethyl, pentafluoroethyl, n- Heptafluoropropyl, n-nonafluorobutyl, n-perfluoropently, n-perfluorohexyl, n- Perfluoroheptyl, n-perfluorooctyl or n-perfluorononyl. In particular preferably m means 1, 2, 3 or 4. In very particularly preferred Embodiments assumes the meaning 1.

The following group of compounds of sub-formulas I1 to I98 represents further preferred embodiments of the invention:

wherein R ¹ , Q, Z, m and A ^{1 have} the meaning given above and L ⁴ , L ⁵ independently of one another are F or H.

If R ¹ in the formulas above and below denotes an alkyl radical and / or an alkoxy radical, this can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably means ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy, furthermore methyl , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl preferably means straight-chain 2-oxapropyl (= methoxy methyl), 2 - (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxa heptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxa nonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R ^{1 is} an alkyl radical in which a CH ₂ group has been replaced by -CH = CH-, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it means particularly 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. If R ^{1 is} an alkyl radical in which one CH ₂ group has been replaced by -O- and one has been replaced by -CO-, these are preferably adjacent. Thus, these contain an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are preferably straight-chain and have 2 to 6 carbon atoms.

Accordingly, they mean especially 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, ethoxy carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxy carbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 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 is replaced by CO or CO-O or O-CO-, this can be straight-chain or be branched. It is preferably straight-chain and has 4 to 13 carbon atoms. Accordingly, it means especially acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxy nonyl, 10-acryloyloxydoxyl, Methacryloyloxy ethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyl oxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoxyctyl, 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 is} an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain and halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F. The resulting residues also include perfluorinated residues. In the case of single substitution, the fluorine or chlorine substituent can be in any position, but preferably in the ω position.

Compounds of the formula I with branched wing group R ¹ can occasionally be important because of their better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components for ferroelectric materials.

Branched groups of this type usually contain no more than one chain branch. Preferred branched radicals R ¹ 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, 1-methylheptyloxy.

Formula I includes both the racemates of these compounds and the optical antipodes and mixtures thereof.

Among these are compounds of formula I and the sub-formulas preferred those in which at least one of those contained therein Radicals has one of the preferred meanings indicated.

In the compounds of formula I are those stereoisomers preferred in which the rings Cyc and piperidine are trans-1,4-disubstituted are. Those of the above formulas, the one or contain several groups Pyd, Pyr and / or Dio, each enclose the two 2,5-position isomers.  

Some very particularly preferred smaller groups of compounds of the formula I are those of the sub-formulas I99 to I151:

wherein R ^{1 is} preferably alkyl, alkoxy, alkenyl or alkenyloxy having 2 to 7 carbon atoms, L ⁴ , L ⁵ preferably do not simultaneously have the meaning H and m is 1, 2, 3 or 4.

Very particularly preferred compounds of this group are those of Formulas I99, I100, I104, I105, I113, I114, I122, I123, I124, I127, I133, I136 and I140.

The compounds of formula I are according to methods known per se presented as they are in the literature (e.g. in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart) are described and under reaction conditions that for the implementations mentioned are known and suitable.

You can do this from known, not mentioned here Make use of variants.  

The perfluoroalkyl tetrafluorosulfanyl ethyne used as the starting compound can e.g. B. in analogy to the literature (J. Wessel, G. Kleemann, K. Sep pelt, Chem. Ber. 116, 2399-2407, 1983, FW Hoover, DD Coffman, J. Org. Chem. 29, 3567-3570, 1964) can be obtained.

can e.g. B. produced in analogy to the literature become (H. Wessolowski, G.-V. Roschenthaler, R. Winter, G.L. Gard, Z. Natural science. 46b, 123-125, 1991). The corresponding unfluorinated or simply fluorinated compounds are also analogous to these Procedure received.

If desired, the starting materials can also be formed in situ are such that they are not isolated from the reaction mixture, but immediately continues to convert to the compounds of formula I.

The synthesis of the compounds of the formula I in which A ¹ denotes axially fluorinated cyclohexane can be carried out by using hydrogen fluoride under pressure or by amine-hydrogen fluoride adducts (e.g. BAV Grosse, CB Linn, J. Org. Chem. 3, (1938 ) 26; GA Olah, M. Nojima, I. Kerekes, Synthesis, (1973) 779; GA Olah, XY. Li, Q. Wang, GKS Prakash, Synthesis (1993) 693).

The compounds of the invention can e.g. B. according to the following Reaction schemes are made:  

Scheme 1

Scheme 2

Esters of the formula I can also be correspondingly esterified Carboxylic acids (or their reactive derivatives) with alcohols or Phenols (or their reactive derivatives) or according to the DCC Method (DCC = dicyclohexylcarbodiimide) can be obtained.

The corresponding carboxylic acids and alcohols or phenols are known or can be prepared in analogy to known methods become.

Suitable reactive derivatives of the carboxylic acids mentioned are especially the acid halides, especially the chlorides and bromides furthermore the anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.  

As reactive derivatives of the alcohols or phenols mentioned come in particular the corresponding metal alcoholates or Phenolates, preferably an alkali metal such as Na or K, into consideration.

The esterification is advantageous in the presence of an inert solvent carried out. Particularly suitable are ethers such as diethyl ether, di-n- butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or Cyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide, Hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons substances such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as Dimethyl sulfoxide or sulfolane. Solvents immiscible with water can also be advantageous for azeotropic distillation of the Esterification water formed can be used. Occasionally can also an excess of an organic base, e.g. B. pyridine, quinoline or Triethylamine, can be used as a solvent for the esterification. The esterification can also be carried out in the absence of a solvent, e.g. B. by simply heating the components in the presence of sodium acetate. The reaction temperature is usually between -50 ° and + 250 °, preferably between -20 ° and + 80 °. At the esterification reactions are usually after these temperatures Ended 15 minutes to 48 hours.

The reaction conditions for the esterification depend in particular largely depends on the nature of the raw materials used. So will a free carboxylic acid with a free alcohol or phenol usually in the presence of a strong acid, for example a mineral acid such as Hydrochloric acid or sulfuric acid. A preferred response is the implementation of an acid anhydride or in particular one Acid chloride with an alcohol, preferably in a basic environment, where as bases in particular alkali metal hydroxides such as sodium or Potassium hydroxide, alkali metal carbonates or bicarbonates such as Sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, Alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as Triethylamine, pyridine, lutidine, collidine or quinoline are important.  

Another preferred embodiment of the esterification is that the alcohol or the phenol first in the sodium or Potassium alcoholate or phenolate transferred, e.g. B. by treatment with ethanolic sodium or potassium hydroxide solution, this isolated and with an acid anhydride or in particular acid chloride.

Nitriles can be replaced by exchanging halogens with copper cyanide or Alkali cyanide can be obtained.

In a further process for the preparation of the compounds of Formula I, in which Z is -CH = CH-, is an aryl halide an olefin in the presence of a tertiary amine and a palladium catalyst (see R.F. Heck, Acc. Chem. Res. 12 (1979) 146). Suitable Aryl halides are, for example, chlorides, bromides and iodides, especially bromides and iodides. The one for the success of the clutch reaction required tertiary amines, such as. B. triethylamine are suitable also as a solvent. Examples of palladium catalysts are its salts, in particular (Pd (II) acetate, with organic phosphorus (III) - Connections such as B. Triarylphosphanen suitable. You can do it in Presence or absence of an inert solvent at tempera structures between about 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, work; come as a solvent, for. B. nitriles such as acetonitrile or Hydrocarbons such as benzene or toluene into consideration. The as an exit Aryl halides and olefins used in materials are widely available on the market available or can be prepared by methods known from the literature be, for example by halogenating the corresponding strain compounds or by elimination reactions on corresponding Alcohols or halides.

In this way, stilbene derivatives can be produced, for example. The Stilbenes can still be made by implementing a 4-substituted benzaldehyde with an appropriate phosphorylide after Wittig. However, tolanes of the formula I can also be prepared by one uses monosubstituted acetylene instead of the olefin (synthesis 627 (1980) or Tetrahedron Lett. 27, 1171 (1986)).  

Furthermore, aryl halides can be coupled with aryl to couple aromatics tin compounds are implemented. These reactions are preferred with the addition of a catalyst such. B. a palladium (0) complex in inert solvents such as hydrocarbons at high temperatures, e.g. B. in boiling xylene, carried out under a protective gas.

Couplings of alkynyl compounds with aryl halides can be carried out analogously that of A.O. King, E. Negishi, F.J. Villani and A. Silveira in J. Org. Chem 43, 358 (1978).

Tolanes of the formula I, in which Z is -C∼C-, can also be obtained via the Fritsch-Buttenberg-Wiechell rearrangement (Ann. 279, 319, 1984) be put in the 1,1-diaryl-2-halogenethylene are rearranged to diarylacetylenes in the presence of strong bases.

Tolanes of formula I can also be prepared by the the corresponding stilbene is brominated and then a dehydrohalo Submission to submission. You can do it in a known way, but not here Apply mentioned variants of this implementation.

Ethers of the formula I can be obtained by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, e.g. B. by treatment with NaH, NaNH ₂ , NaOH, KOH, Na ₂ CO ₃ or K ₂ CO _{3 is converted} into the corresponding alkali metal alcoholate or alkali metal phenolate. This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as. B. acetone, 1,2-dimetho xythan, DMF or dimethyl sulfoxide or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° C and 100 ° C.

For the production of laterally substituted fluorine or chlorine compounds of the formula I corresponding aniline derivatives with sodium nitrite and either with tetrafluoroboric acid (to introduce an F atom) or with  Copper (I) chloride (to introduce a Cl atom) to the diazonium salt are implemented, which then thermally at temperatures of 100 ° -140 ° be decomposed.

Linking an aromatic core with a non-aromatic one Core or two non-aromatic nuclei are preferably obtained by Condensation of a lithium or organomagnesium compound with a ketone if there is an aliphatic group Z between the nuclei should.

The organometallic compounds are put through, for example Metal-halogen exchange (e.g. according to Org. React. 6, 339-366 (1951)) between the corresponding halogen compound and a lithium organic compound such as preferably tert-butyllithium or lithium Naphthalenide or by conversion with magnesium shavings.

The linking of two aromatic rings or aliphatic group Z with an aromatic ring is preferably carried out by Friedel-Crafts alkylation or acylation by reacting the corresponding aromatic compounds with Lewis acid catalysis. Appropriate Lewis acids are e.g. B. SnCl ₄ , ZnCl ₂ or especially AlCl ₃ and TiCl ₄ .

Furthermore, the connection of two aromatic rings can be made through the Ullmann reaction (e.g. Synthesis 1974, 9) between aryl iodides with Copper iodide, but preferably between an aryl-copper compound and an aryl iodide, or by the Gomberg-Bachmann reaction between an aryl diazonium salt and the corresponding aroma table connection (e.g. Org. React. 2, 224 (1944)). The Representation of the tolanes of formula I (Z = -C∼C-) z. B. by Implementation of the corresponding arylhologenides with an acetylide in a basic solvent with transition metal catalysis; prefers Palladium catalysts can be used here, especially one Mixture of bis (triphenylphosphine) palladium (II) chloride and copper iodide in Piperidine as a solvent.  

In addition, the compounds of the formula I can be prepared by adding a compound which otherwise corresponds to the formula I Instead of H atoms, one or more reducible groups and / or Contains C-C bonds, reduced.

As reducible groups are preferably carbonyl groups, in particular keto groups, further z. B. free or esterified hydroxyl groups or aromatic halogen atoms. Preferred starting materials for the reduction are compounds corresponding to the formula I, but instead of a cyclohexane ring a cyclohexene ring or cyclohexanone ring and / or instead of a -CH ₂ CH ₂ group a -CH = CH group and / or instead of a -CH ₂ group contain a -CO group and / or instead of an H atom a free or a functionally modified (e.g. in the form of its p-toluenesulfonate) OH group.

The reduction can e.g. B. done by catalytic hydrogenation at temperatures between about 0 ° and about 200 ° and pressures between about 1 and 200 bar in an inert solvent, for. B. an alcohol such as methanol, ethanol or isopropanol, an ether such as tetrahydrofuran (THF) or dioxane, an ester such as tetrahydrofuran (THF) or dioxane, an ester such as ethyl acetate, a carboxylic acid such as acetic acid or a hydrocarbon such as cyclohexane. Suitable catalysts are suitably noble metals such as Pt or Pd, which can be used in the form of oxides (e.g. PtO ₂ , PdO), on a support (e.g. Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form .

Ketones can also by the methods of Clemmensen (with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in aqueous alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °) or Wolff-Kishner (with hydrazine, expedient in the presence of alkali such as KOH or NaOH in a high-boiling solvent such as diethylene glycol or triethylene glycol at temperatures between about 100 and 200 °) to the corresponding compounds of formula I, which contain alkyl groups and / or -CH ₂ CH ₂ bridges will.

Reductions with complex hydrides are also possible. For example, arylsulfonyloxy groups can be removed reductively with LiAIH ₄ , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, expediently in an inert solvent such as diethyl ether or THF at temperatures between about 0 and 100 °. Double bonds can be hydrogenated with NaBH ₄ or tributyltin hydride in methanol.

The starting materials are either known or can be made in analogy be made to known compounds.

The liquid-crystalline media according to the invention preferably contain in addition to one or more compounds according to the invention as further Components 2 to 40, especially 4 to 30 components. Very special more preferably, these media contain one or more inventions compounds according to the invention 7 to 25 components. These others Components are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular Substances from the classes of azoxybenzenes, benzylidene anilines, Biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane phenyl or cyclohexyl carboxylate, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclo hexylcyclohexane carboxylic acid, cyclohexyl phenyl ester of benzoic acid, cyclohexane carboxylic acid or cyclohexylcyclohexane carboxylic acid, Phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, Cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclo hexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexyl pyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyl dioxanes, phenyl- or cyclohexyl-1,3-dithiane, 1,2-diphenylethanes, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylihane, 1-cyclohexyl-2- (4- phenyl-cyclohexyl) -ethane, 1-cyclohexyl-2-biphenylylethane, 1-phenyl-2- cyclohexyl-phenylethane, optionally halogenated stilbene, benzyl phenyl ether, tolanes and substituted cinnamic acids. The 1,4-phenylene Groups in these compounds can also be fluorinated.  

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

R'-LE-R '' 1
R'-L-COO-E-R '' 2
R'-L-OOC-E-R '' 3
R'-L-CH ₂ CH ₂ -E-R "4
R'-LC = CE-R '' 5.

In formulas 1, 2, 3, 4 and 5, L and E mean the same or ver can be different, each independently a bivalent Balance from the from -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr- -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, where Phe is 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 and G 2- (trans-1,4-cyclo hexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl mean.

One of the radicals L and E is preferably Cyc, Phe or Pyr. E is in front preferably Cyc, Phe or Phe-Cyc. Preferably contain the inventions media according to the invention selected one or more components the compounds of formulas 1, 2, 3, 4 and 5, wherein L and E are selected are from the group Cyc, Phe and Pyr and simultaneously one or more Components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the rest of the rest is selected from the group -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and given if one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.  

R 'and R' 'in a smaller subset of the compounds of the Formulas 1, 2, 3, 4 and 5 each independently of the other alkyl, alkenyl, Alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy with up to 8 carbon atoms. This smaller subgroup is called Group A below and the compounds are represented by sub-formulas 1a, 2a, 3a, 4a and 5a designated. For most of these compounds, R 'and R' 'are the same others different, one of these radicals mostly alkyl, alkenyl, alkoxy or alkoxyalkyl.

In another smaller subgroup, referred to as group B, of the compounds of the formulas 1, 2, 3, 4 and 5, R '' is -F, -Cl, -NCS or - (O) _i CH _{3- (k + l)} F _k Cl _l , where i is 0 or 1 and k and l are 1, 2 or 3; the compounds in which R '' has this meaning are designated by the sub-formulas Ib, 2b, 3b, 4b and 5b. Those compounds of partial formulas 1b, 2b, 3b, 4b and 5b in which R ″ has the meaning -F, -Cl, -NCS, -CF ₃ , -OCHF ₂ or -OCF _{3 are} particularly preferred.

In the compounds of sub-formulas 1b, 2b, 3b, 4b and 5b, R 'has the at the compounds of the sub-formulas 1a-5a and meaning preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.

In a further smaller subgroup of the compounds of the formulas 1, 2, 3, 4 and 5 means R '' - CN; this subgroup is hereinafter referred to as Group C designated and the compounds of this subgroup described accordingly with sub-formulas 1c, 2c, 3c, 4c and 5c. In the Compounds of the sub-formulas 1c, 2c, 3c, 4c and 5c have R 'those in the Compounds of sub-formulas 1a-5a given meaning and is preferably alkyl, alkoxy or alkenyl.

In addition to the preferred compounds of groups A, B and C are also other compounds of formulas 1, 2, 3, 4 and 5 with other variants of the proposed substituents in use. All of these substances are obtainable according to methods known from the literature or in analogy.  

In addition to the compounds of the formula I according to the invention, the media according to the invention preferably contain one or more compounds which are selected from group A and / or group B and / or group 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%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in particular 10 to 65%
Group C: 0 to 80%, preferably 5 to 80%, in particular 5 to 50%

where the sum of the mass fractions of the invention in each according to media contained compounds from groups A and / or B and / or C preferably 5% -90% and in particular 10% to 90% is.

The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30% of the verb according to the invention fertilize. Media containing more than 40% are also preferred. in particular 45 to 90% of compounds according to the invention. The Media preferably contain three, four or five according to the invention Links.

The media according to the invention are produced in a manner which is customary per se Wise. As a rule, the components are dissolved into one another, for this purpose moderate at elevated temperature. With suitable additives, the liquid crystalline phases are modified according to the invention so that it in all types of liquid crystal display that have become known elements can be used. Such additives are Known to those skilled in the art 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 used for production colored guest host systems or substances to change the dielectric anisotropy, viscosity and / or orientation of the nematic phases are added.

The following examples are intended to illustrate the invention without limiting it. Percentages above and below mean percentages by weight. All temperatures are given in degrees Celsius. Mp. Means melting point Klp. = Clearing point. Furthermore, K = crystalline state, N = nematic phase, Sm = smectic phase and I = isotropic phase. The information between these symbols represents the transition temperatures. Δn means optical anisotropy (589 nm 20 ° C) and Δε the dielectric anisotropy (1 kHz, 20 ° C). The viscosity (mm ² / sec) was determined at 20 ° C.

"Normal work-up" means: if necessary, water is added, extracted with methylene chloride, diethyl ether or toluene, separates, dries the organic phase, evaporates and purifies the product by distillation lation under reduced pressure or crystallization and / or chromato graph.

The following abbreviations are used:
THF: tetrahydrofuran
KOtBu: Potassium tert-butoxide
RT: room temperature
MTB ether: methyl tert-butyl ether.

example 1

A mixture of 30 mmol 1, 30 mmol 2, 0.6 mmol Bis (triphenylphosphine) palladium dichloride, 0.3 mmol Cul and 60 ml Triethylamine is stirred in the inclusion tube at RT for 18 h. The approach is going worked up as usual and the product 3 purified by chromatography.

A mixture of 30 mmol 3, 30 mmol 4, 0.6 mmol tetrakis (triphenyl phosphine) palladium, 160 ml water, 25 ml 32% aqueous NaOH and 320 ml of toluene is heated to reflux for 18 h. The approach is as usual worked up and the product 5 purified by chromatography.  

Example 2

A solution of 30 mmol 3 in 10 ml THF is at -78 ° C with 30 mmol BuLi (1.6 M in THF) metalized. After 30 min. become 30 mmol 4-Propylcyclohexanone added dropwise in 50 ml of THF. You let come to RT and works up watery. The crude product is in 300 ml of toluene Add 0.5 g of p-toluenesulfonic acid boiled on a water separator. Man works up watery again after the end of the water separation and hydrogenate the crude intermediate in THF with 1 g of 5% Pd-C until the end the hydrogen uptake. After the usual work-up, one obtains the product 6 by crystallization from heptane or ethanol.

Example 3

A solution of 30 mmol 3 in 10 ml THF is added dropwise at -78 ° C 30 mmol BuLi (1.6 M in THF) were added. After 30 min. become 30 mmol DMF added dropwise, and the mixture is allowed to slowly come to RT. It will worked up as usual and the product 7 chromatographically purified.  

A mixture of 30 mmol 7, 30 mmol 2-propylpropane-1,3-diol, 0.5 g p-Toluenesulfonic acid and 300 ml of toluene is added to the end Boiled water separation on the water separator. You work on how usual and isolates the pure product 8 by crystallization from heptane.

Analogously, the corresponding preliminary stages become the following Compounds according to the invention receive:

Example 4-40

Example 41-56

Example 57-82

Example 83-98

Claims (10)

1. Perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I.
R ¹ - (A ¹ Z) _n -AQ-SF ₄ C _m F _{2m + 1} I
wherein
R ¹ H, an unsubstituted, a simply by CN or CF ₃ or an at least mono-substituted alkyl radical with 1-12 carbon atoms or alkenyl radical with 2-12 carbon atoms, in which radicals one or more non-adjacent CH ₂ groups can each be replaced independently of one another by -O-, -S -, - CO-, -CO-O-, -O-CO- or -O-CO-O-,
A ¹ , A one

• a) trans-cyclohexane-1,4-diyl radical, in which one or more non-adjacent CH ₂ groups can also be replaced by -O- and / or -S-,
• b) 1,4-phenylene radical, in which one or two CH groups can also be replaced by N,
• c) residue from the group 1,4-bicyclo (2,2,2) octylene, pipidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2, 3,4-tetrahydronaphthalene-2,6-diyl,
• d) cyclohexene-1,4-diyl

where the radicals a), b) and d) can be substituted by CN, Cl or F,
X ¹ , X ² each independently of one another H or F,
Z -CO-O-, -O-CO-, -CH ₂ O-, -O-, -O-CH ₂ , -CH ₂ CH ₂ -, -CH = CH-, -C∼C-, a single bond ,
u 1, 2 or 3
v 2, 3 or 4
n 1, 2 or 3
and
m 1 to 10
means. 2. perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I according to claim 1, characterized in that m has the meaning 1, 2, 3 or 4 assumes. 3. perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I according to claim 1, characterized in that Q takes the meaning -C∼C-.   4. Perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I according to claim 1, 2 or 3, characterized in that R ¹ denotes straight-chain alkyl or alkoxy having 1 to 10 C atoms or alkenyl or alkenyloxy having 2 to 10 C atoms. 5. Perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I according to claim 1, 2, 3 or 4, characterized in that R ^{1 is} straight-chain alkyl or alkoxy having 1 to 10 C atoms or alkenyl or alkenyloxy having 2 to 10 C atoms and A is the meaning
having. 6. Perfluoroalkyl tetrafluorosulfanyl derivatives of the formula I according to claim 1 to 5, characterized in that the radicals Z -CH ₂ CH ₂ -, -CH = CH-, -C∼C-, -CF ₂ CF ₂ -, -CF = CF or a single bond mean. 7. Use of compounds of formula I according to claim 1 to 6 as components of liquid crystalline media. 8. Liquid-crystalline medium with at least two liquid-crystalline ones Components, characterized in that there is at least one Contains compound of formula I. 9. Liquid crystal display element, characterized in that it is a contains liquid-crystalline medium according to claim 8. 10. Electro-optical display element, characterized in that it as a dielectric, a liquid-crystalline medium according to claim 8 contains.