DE3408802A1 - Liquid-crystalline sulphur oxide derivatives - Google Patents

Abstract

The invention relates to sulphur-oxide containing, liquid-crystalline compounds of the formula I R<1>-(A<1>)m-Z-(A<2>)n-R<2> in which the group Z is -(CH2)s-Z<2>-(CH2)t-, and, in this formula, the group Z<2> according to the invention is -SO-, -SO2-, -SO2-SO2-, -SO2-O-, -SO2-S-, -SO2-NR<4>. S and t can in each case assume values of 0, 1 or 2. Furthermore, R<1> and R<2> are in each case H, an alkyl group having 1-10 C atoms in which one or two non-adjacent CH2 groups can also be replaced by O-atoms, or are -COOR, -OCOR, F, Cl, Br, CN, SR, SOR, SO2R or R<3>-A<3>-Z<1>, where only R<1> or R<2> can be H or R<3>-A<3>-Z<1>-, R is an alkyl group having 1-10 C atoms, A<1>, A<2>, A<3> are in each case 1,4-phenylene groups which are unsubstituted or substituted by one or two F and/or Cl atoms and/or Br atoms and/or CH3 groups and/or CN groups, in which one or two =CH-groups can optionally be replaced by =N-, or are 1,4-cyclohexylene groups in which one or two non-adjacent CH2 groups can optionally be replaced by O, or are 1,3-dithiane-2,5-diyl, piperidine-1,4-diyl or 1,4-bicyclo(2,2,2)octylene groups, Z<1> is -COO-, -O-CO-, -CH2-CH2-, -OCH2-, -CH2O, Z or a single bond, R<3> is H, an alkyl group having 1-10 C atoms in which one or two non-adjacent CH2 groups can also be replaced by O atoms, or is F, Cl, Br, CN, -COOR, -OCOR, SR, SOR or SO2R, R<4> is H or an alkyl group having 1-5 ... Original abstract incomplete.

Description

Liquid crystalline sulfur oxide derivatives

Liquid crystalline sulfur oxide derivatives The invention relates to sulfur oxide-containing, liquid-crystalline compounds of the formula I R¹- (A¹) m-Z- (A²) n-R² I wherein the group Z - (CH2) S-Z - (CH2) t-, and therein the group according to the invention Z² -SO-, SO2, SO2 SO2 , -SO2-O-, SO2 S, -SO2-NR4- means. S and t can take the values 0, 1, or, respectively 2 accept.

Furthermore, R1 and R2 each denote H, an alkyl group with 1-10 C atoms, in which one or two non-adjacent CH2 groups are replaced by O atoms -COOR, -OCOR, F, C1, Br, CN, SR, SOR, SO2R or R3-A3-Z1-, where only R1 or R2 may be H or R3-A3-Z1-, R is an alkyl group with 1 - 10 carbon atoms, A1, A2, A3 each unsubstituted or by one or two F and / or Cl atoms and / or Br atoms and / or CH3 groups and / or CN groups substituted 1,4-phenylene groups, where optionally one or two = CH groups can be replaced by = N-, 1,4-cyclohexylene groups, in which optionally one or two non-adjacent CH2 groups are replaced by 0 can be 1,3-dithiane-2,5-diyl, piperidine-1,4-diyl or 1,4-bicyclo (2,2,2) octylene groups, Z¹ -COO-, -O-CO-, -CH2-CH2-, -OCH2-, -CH2O, Z or a single bond, R3 H, a Alkyl group with 1 - 10 carbon atoms, in which one or two non-adjacent CH2 groups replaced by O atoms can be, F, C1, Br, CN, -COOR, -0C0R, SR, SOR or SO2R 4 R H or alkyl group with 1 - 5 carbon atoms, m and n each 1 or 2, where for m = 2 and / or A1 and / or A2 n = 2, the groups are identical to or from one another can be different.

For the sake of simplicity, in the following Phe denotes a 1,4-phenylene group, Cy is a 1,4-cyclohexylene group, Dio is a 1,3-dioxane-2,5-diyl group, Dit is a 1,3-dithiane-2,5-diyl group, Bi is a 1,4-bicyclo (2,2,2) octylene group, Pip is a piperidine-1,4-diyl group, Pyn a pyridazine-3,6-diyl group and Pyr a pyrimidine-2,5-diyl group, Phe being unsubstituted or by one or two F and / or Cl and / or Br atoms and / or CH3 groups and / or CN groups can be substituted.

The compounds of the formula I can be liquid-crystalline components as components Phases are used, especially for displays, which are based on the principle of twisted Cell, the guest-host effect, the effect of deformation of erect phases or based on the effect of dynamic scattering.

For the technical application of these effects in electronic components liquid-crystalline phases are required that meet a large number of requirements have to suffice. Chemical resistance is particularly important here Moisture, atmospheric oxygen and physical influences such as heat, infrared and ultraviolet radiation as well as electric constant and alternating fields. Further becomes as large as possible of technically usable liquid-crystalline phases liquid crystalline mesophase range (low melting points, high clearing points), associated with a The lowest possible viscosity is required. In the end such compounds should be colorless if possible.

Usually mixtures of two or more compounds are used produced, as by the selection of suitable liquid-crystalline components in such mixtures in the desired way influence physical properties such as for example melting and clearing point, solubility, viscosity, dielectric and optical anisotropy can be taken.

The invention was based on the object of providing new stable liquid-crystalline or to find mesogenic compounds that are liquid-crystalline components Phases are suitable.

It has been found that the compounds of formula I as components liquid-crystalline phases are eminently suitable. In particular, are with their Help stable liquid crystalline phases with higher depending on the chemical constitution negative or positive dielectric anisotropy, electro-optical effects, cheaper optical anisotropy and usable low viscosity can be produced. they are therefore also suitable for the production of multiplexable mixtures. Such liquid crystalline Electro-optical cells containing phases have favorable threshold or control voltage and good steepness of the characteristic curve.

Due to the optionally more or less polar sulfur-containing The compounds of the formula I show group Z and z2, in part surprising high dissolving power for polar compounds such as dopants, salts, dyes and optically active dopants. For example, the solubility of dyes commonly used for these purposes in liquid-crystalline mixtures which contain at least one of the compounds of the formula I, depending on Increase amount by 5 to 70%, preferably 10-50%. As depending on the choice of the groups Z and z2, also other physical properties, varied within certain limits can be, with the provision of the compounds of the formula I is a subordinate considerably broadened, suitable for the various application-related aspects Range of liquid crystalline substances available.

The compounds of the formula I have a wide range of applications. Depending on the choice of substituents, these compounds can be used as Base materials are used, from which liquid-crystalline phases are predominantly used are composed; however, compounds of the formula I can also be liquid-crystalline Base materials from other classes of compounds can be added, for example to lower the dielectric and / or optical anisotropy of such a dielectric. The compounds of the formula I are also suitable as intermediates for the preparation other substances that are used as components of liquid-crystalline phases permit.

The compounds of the formula I are colorless in the pure state and form liquid crystalline mesophases in one favorable for electro-optical use located temperature range. They are very stable chemically, thermally and against light.

The invention thus relates to compounds of the formula I and Process for their manufacture. The production can e.g. B. be done so that one for the preparation of sulfoxides of the formula I (in which z2 is -SO-) the corresponding Thioethers oxidized, or that for the preparation of sulfones of the formula I (in which Z2 502 - means) the corresponding thioethers oxidized or the corresponding Sulphonic acids or one of their reactive derivatives with organometallic compounds or if necessary with. corresponding aryl hydrocarbons or corresponding Sulfinates reacts with halides, or that one can produce Disulfones of the formula I (in which z2 is - (SO2) 2-) the corresponding sulfinic acids oxidized or the corresponding sulfonyl halides with the corresponding sulfinates or with alkali metal, or that one for the preparation of sulfonic acid esters of formula I (in which Z2-SO2O-) the corresponding sulfonic acids or one their reactive derivatives with the corresponding alcohols or their reactive derivatives Reacts derivatives, or that one for the preparation of thiosulfonic acid esters of the formula I (where Z2-SO2S-) oxidizes the corresponding disulfides or the corresponding Sulfenyl halides are reacted with the corresponding sulfinates, or that one for the preparation of sulfonamides of the formula I (in which Z2 is SO2NR4- and R4 is the meaning given has) the corresponding sulfonic acids or their reactive derivatives with corresponding Amines converts or corresponding sulfonamides of the formula R ° -SO2NH (where RO is R1- (A1) - (CH2) 5- or R2- (A2) n- (CH2) t- and R, R, A, A, n, m, s and t have the meanings given), with a corresponding halide converts, or that a compound which otherwise corresponds to formula I, but on Place one or more reducible groups and / or C-C bonds instead of H atoms contains, treated with a suitable reducing agent, or that one for preparation of esters of the formula I (in which R1 and / or R2 and / or R3 -OCOR- and / or -COOR mean and / or zl -COO- or -OCO- means) a corresponding carboxylic acid or one of their reactive derivatives with a corresponding alcohol or a its reactive derivatives converts, or that one for the production of ethers of the formula I (in which R1 and / or R2 and / or R3 represent an alkoxy group) corresponding hydroxy compounds are etherified, or that one can produce dioxane derivatives of the formula I (in which A1 and / or A2 and / or A3 are 1,3-dioxane-2,5-diyl) a corresponding aldehyde is reacted with a corresponding diol, or that one for the preparation of nitriles of the formula I (in which R1 and / or R2 and / or R3 are CN, and / or wherein A1 and / or A2 and / or A3 is substituted by at least one CN group) a corresponding carboxamide is dehydrated or a corresponding halide with a cyanide or a corresponding carboxylic acid halide with sulfamide converts, and / or that, if appropriate, a base of the formula I by treatment converts with an acid into one of its acid addition salts, or that optionally a compound of the formula I from one of its acid addition salts released by treatment with a base.

The invention also relates to the use of the compounds of the formula I as components of liquid-crystalline phases.

The invention also relates to liquid-crystalline phases with a content of at least one compound of the formula I and liquid crystal display elements, in particular electro-optical display elements that contain such phases.

Above and below have R1, R2, R3, R4, A1, A2, Z, 7 z2, m, n, s and t have the meanings given, unless expressly stated otherwise is.

The compounds of Formula I include compounds of the following Part formulas Ia - Ii.

R1- (A1) m -Z2- (A2) n-R2 Ia R1- (A1) m -CH2 -Z2- (A2) -n-R2 Ib R1- (A1) m -Z2 -CH2- (A2) n -R² Ic R¹- (A¹) m-CH2-Z²-CH2- (A²) n-R2 Id R¹- (A¹) m-CH2-CH2-Z²- (A²) n-R² Ie R¹- (A¹) m-Z²- CH2-CH2- (A2 9n-R2 If R¹- (A¹) m-CH2-CH2-Z²-CH2- (A²) n-R² Ig R¹- (A¹) m-CH2-Z²-CH2-CH2- (A²) n-R² Ih R¹- (A¹) m-CH2-CH2-Z²-CH2-CH2- (A²) n -R² Ii Of these, those of the sub-formulas Ia, Ib, Ic and Id are preferred, in particular Ib and Ic (In the event that z2 means -SO-, -SO2- or - (SO2) 2-, the sub-formulas are Ib and Ic, Ie and If as well as Ig and Ih are identical).

The preferred compounds of the sub-formulas Ia-Id thus include those of the sub-formulas Ia, b, c, d (m, n) R¹- (A¹) m-Z- (A²) n-R², where m and n are the Number of ring groups A1 or A2 on one or the other side of the bridge member Specify Z or Z². In detail: R¹-A¹-Z²-A²-R² I a (1,1) R¹- (A¹) 2-Z²-A²-R² I a (2.1) R¹-A¹-Z²- (A²) 2-R² I a (1,2) R¹- (A¹) 2-Z²- (A²) 2-R² I a (2.2) R¹-A¹- CH2-Z²-A²-R² Ib (1,1) R¹- (A¹) 2-CH2-Z²-A²-R² I b (2,1) R¹-A¹-CH2-Z²- (A²) 2-R² I b (1,2) R¹ - (A¹) ²-CH2-Z²- (A²) 2-R² I b (2.2) R¹-A¹-Z²-CH2-A²-R² I c (1.1) R¹- (A¹) 2-Z²-CH2-A²-R² I c (2,1) R¹-A¹- Z²-CH2- (A²) 2-R² I c (1,2) R¹- (A¹) 2-Z²-CH2- (A²) 2-R² I c (2.2) R¹-A¹-CH2-Z²-CH2-A²-R² I d (1.1 ) R¹- (A¹) 2-CH2-Z²-CH2-A²-R² Id (2,1) R¹-A¹-CH2-Z²- (CH2- (A²) 2-R² I d (1,2) R¹- (A¹) 2-CH2-Z²-CH2- (A²) -R² I d (2.2) For the sake of simplicity, the formula complexes are used below, unless otherwise noted Ia (m, n), Ib (m, n), Ic (m, n) and Id (m, n) in their entirety by the formula I (m, n) shown in abbreviated form. In addition, Z has the meaning defined for a-d (-Z²-, -CH2-Z²-, -Z²-CH2-, -CH2-Z²-CH2-).

The preferred compounds of the sub-formulas I (1,1) include under other those of the sub-formulas I (1,1) 1- I mentioned as preferred below (1,1) 26 R1-Phe-Z-Phe-R2 I (1,1) 1 R1-Phe-Z-Cy-R2 "lt 2 R¹-Phe-Z-Dio-R²" "3 R¹-Phe- Z-Pyr-R² "" 4 R¹-Phe-Z-Pip-R² "" 5 R¹-Phe-Z-Bi-R² "" 6 R¹-Phe-Z-Dit-R² "" 7 R¹-Phe-Z-Pyn-R² "" 8 R¹-Cy-Z-Phe-R² "" 9 R¹-Cy-Z-Cy-R² "" 10 R¹-Phe-Z-Dio-R² is <11 R¹-Phe-Z-Pyr-R² "" 12 R¹-Phe-Z-Pip-R² lt II 13 R¹-Cy-Z-Bi-R² "" 14 R¹-Dio-Z-Phe-R² "" 15 R¹-Dio-Z-Cy-R² "" 16 R¹-Dio-Z-Dio-R² "" 17 R¹-Dio-Z-Pyr-R² "" 18 R¹-Dio-Z-Pip-R² "" 19 R¹-Dio-Z-Bi-R² "" 20 R¹-Pyr-Z-Phe-R² "" 21 R¹-Pyr-Z-Cy-R² "" 22 R¹-Pyr-Z-Dio-R² "" 23 R¹-Pyr-Z-Pyr-R² "" 24 R¹-Pyr-Z-Bi-R² "" 25 R¹-Pyr-Z-Pip-R² "" 26 Among them are those compounds particularly preferred in which A1 and A2 are different from one another, in particular not are Phe at the same time.

The preferred compounds of the sub-formulas I (1,2) include among others those of the sub-formulas I (1, 2) 1 bis preferably mentioned below I (1,2) 44, R1-Phe-Z-Phe-Phe-R2 I (1,2) 1 R1 -Phe-Z-Cy-Phe-R2 7 lt 2 R¹-Phe-Z-Phe-Cy- R² "" 3 R¹-Phe-Z-Phe-Dio-R² "" 4 R¹-Phe-Z-Dio-Phe-R² "" 5 R1-Phe-Z-Cy-Cy-R2 according to II 6 R¹-Phe-Z-Cy-Dio-R² "" 7 R¹-Phe-Z-Dio-Cy-R² "" 8 R¹-Phe-Z-Phe-Bi-R² "" 9 R¹-Phe-Z-Bi -Phe-R² "" 10 R¹-Phe-Z-Phe-Pyr-R² "" 11 R¹-Phe-Z-Pyr-Phe-R² "" 12 R¹-Cy-Z-Phe-Phe-R² " "13 R¹-Cy-Z-Phe-Cy-R²" "14 R¹-Cy-Z-Cy-Phe-R²" "15 R¹-Cy-Z-Cy-Cy-R²" "16 R¹-Cy-Z- Cy-Dio-R² "" 17 R¹-Cy-Z-Phe-Dio-R² "" 18 R¹-Cy-Z-Dio-Cy-R² "" 19 R¹-Cy-Z-Dio-Phe-R² "" 20 R¹-Cy-Z-Phe-Pyr-R² "" 21 R¹-Cy-Z-Pyr-Phe-R² "" 22 R¹-Cy-Z-Phe-Bi-R² "" 23 R¹-Cy-Z-Bi- Phe-R² "" 24 R1-Cy-Z-Bi-Cy-R2 lt lt 25 R¹-Cy-Z-Cy-Bi-R² "" 26 R¹-Dio-Z-Phe-Phe-R² "" 27 R¹-Dio-Z-Phe-Cy-R² "" 28 R¹-Dio-Z-Cy-Phe-R² "" 29 R¹-Dio-Z-Cy-Dio-R² "" 30 R¹-Dio-Z-Dio-Cy-R² I (1,2) 31 R¹-Dio-Z-Cy-Cy-R² "" 32 R¹-Dio-Z-Phe-Dio-R² "" 33 R¹-Dio-Z-Dio-Phe-R² "" 34 R¹-Dio-Z-Phe-Pyr-R² "" 35 R¹-Dio-Z-Pyr-Phe-R² "" 36 R¹-Pyr-Z-Phe-Phe-R² "" 37 R¹-Pyr-Z-Phe-Cy-R² "" 38 R¹-Pyr-Z-Cy-Phe-R² "" 39 R¹-Pyr-Z-Cy-Cy-R² "" 40 R¹-Pyr-Z-Phe-Dio-R² "" 41 R¹-Pyr-Z-Dio-Phe-R² "" 42 R¹-Pyr-Z-Cy-Dio-R² "" 43 R¹-Pyr-Z-Dio-Cy-R² "" 44 The preferred compounds of sub-formula I (2.1) include, among others, those of the sub-formulas preferably mentioned below I (2,1) 1 to I (2,1) 46.

R¹-Phe-Phe-Z-Phe-R² I (2,1) 1 R¹-Phe-Phe-Z-Cy-R² "" 2 R¹-Phe-Phe-Z-Dio-R² "" 3 R¹-Phe-Phe-Z-Pyr-R² "" 4 R¹-Phe-Phe-Z-Bi-R² "" 5 R¹-Phe-Phe-Z-Pip-R² "" 6 R¹-Cy-Phe-Z-Phe-R² "" 7 R¹-Cy-Phe-Z-Cy-R² "" 8 R¹-Cy-Phe-Z-Dio-R² "" 9 R¹-Cy-Phe-Z -Pyr-R² "" 10 R¹-Cy-Phe-Z-Bi-R² "" 11 R¹-Phe-Cy-Z-Phe-R² "" 12 R¹-Phe-Cy-Z-Cy-R² "" 13 R¹-Phe-Cy-Z-Dio-R² "" 14 R¹-Phe-Cy-Z-Pyr-R² "" 15 R¹-Phe-Cy-Z-Bi-R² "" 16 R¹-Cy-Cy-Z-Phe-R² I (2,1) 17 R²-Cy-Cy-Z-Cy-R² "" 18 R²-Cy-Cy-Z-Dio-R² lt lt lt 19 R2 -Cy-Cy-Z-Pyr-R2 20 lt 20 R²-Cy-Cy-Z-Bi-R² lt lt 21 R²-Cy-Cy-Z-Pip-R² Ii lt 22 R¹-Phe-Dio-Z-Phe-R² "" 23 R¹-Phe-Dio-Z-Cy-R² "" 24 R¹-Phe-Dio-Z-Dio-R² "" 25 R¹-Phe-Dio-Z-Pyr-R² "" 26 R¹-Dio-Phe-Z-Phe-R² "" 27 R¹-Dio-Phe-Z-Cy-R² "" 28 R¹-Dio-Phe-Z-Dio-R² "" 29 R¹-Dio-Phe-Z-Pyr-R² "" 30 R¹-Phe-Pyr-Z-Phe-R² "" 31 R¹-Phe-Pyr-Z-Cy-R² "" 32 R¹-Phe-Pyr-Z-Dio-R² "" 33 R¹-Phe-Pyr-Z-Pyr-R² "" 34 R¹-Pyr-Phe-Z-Phe-R² according to 35 R¹-Pyr-Phe-Z-Cy-R² "" 36 R¹-Pyr-Phe-Z-Dio-R² "" 37 R¹-Pyr-Phe-Z-Pyr-R² "" 38 R¹-Cy-Dio-Z-Phe-R² "" 39 R¹-Cy-Dio-Z-Cy-R² "" 40 R¹-Cy-Dio-Z-Dio-R² "" 41 R¹-Cy-Dio-Z- Pyr-R² "" 42 R¹-Dio-Cy-Z-Phe-R² "" 43 R¹-Dio-Cy-Z-Cy-R² "" 44 R¹-Dio-Cy-Z-Dio-R² "" 45 R¹-Dio-Cy-Z-Pyr-R² "" 46 comprise the preferred compounds of sub-formulas I (2,2) including those of the sub-formulas I (2.2) mentioned below as preferred 1 to I (2,2) 39.

R¹-Phe-Phe-Z-Phe-Phe-R² I (2.2) 1 R¹-Cy-Cy-Z-Phe-Cy-R² "" 12 R¹-Phe-Phe-Z-Cy-Phe-R² "" 3 R¹-Phe-Phe-Z-Cy-Cy-R² "" 4 R¹-PHe-Cy-Z-Phe-Phe-R² "" 5 R¹-Phe-Cy-Z-Phe-Cy-R² "" 2 R¹-Cy-Phe-Z-Phe-Phe-R² "" 7 R¹-Cy-Phe-Z-Cy-Phe-R² "" 8 R¹-Cy-Phe-Z-Phe-Cy-R² "" 9 R¹-Cy-Phe-Z-Cy-Cy-R² "" 10 R¹-Phe-Cy-Z-Cy-Cy-R² "" 11 R¹-Cy-Cy-Z-Cy-Phe-R² "" 12 R¹-Cy-Cy-Z-Phe-Cy-R² "" 13 R¹-Cy-Cy-Z-Phe-Phe-R² "" 14 R¹-Phe-Dio-Z-Phe-Phe-R² "" 15 R¹-Phe-Dio-Z-Phe-Cy-R² "" 16 R¹-Dio-Phe-Z-Phe-Cy-R² "" 17 R¹-Phe-Dio-Z-Cy-Phe-R² "" 18 R¹-Phe-Dio-Z-Cy-Cy-R² "" 19 R¹-Dio-Phe-Z-Cy-Cy-R² "" 20 R¹-Dio-Phe-Z-Cy-Phe-R² "" 21 R¹-Phe-Dio-Z-Phe-Phe-R² "" 22 R¹-Dio-Phe-Z-Phe-Phe-R² "" 23 R¹-Phe-Phe-Z-Phe-Dio-R² "" 24 R¹-Phe-Phe-Z-Dio-Phe-R² "" 25 R¹-Phe-Cy-Z-Phe-Dio-R² "" 26 R¹-Phe-Cy-Z-Dio-Phe-R² "" 27 R¹-Cy-Phe-Z-Dio-Phe-R² "" 28 R¹-Cy-Phe-Z-Phe-Dio-R² "" 29 R¹-Cy-Cy-Z-Phe-Dio-R² "" 30 R¹-Cy-Cy-Z-Dio-Phe-R² "" 31 R¹-Phe-Phe-Z-Cy-Dio-R² "" 32 R¹-Phe-Phe-Z-Dio-Cy-R² "" 33 R¹-Phe-Cy-Z-Cy-Dio-R² "" 34 R¹-Phe-Cy-Z-Dio-Cy-R² "" 35 R1-Cy-Phe-Z-Cy-Dio-R2 I (2.2) 36 R¹-Cy-Phe-Z-Dio-Cy-R² "" 37 R¹-Cy-Cy-Z-Cy-Dio-R² "" 38 R¹-Cy-Cy-Z-Dio-Cy -R² "" 39 In the compounds of the formulas above and below, if not otherwise agreed, groups A and / or A2 in the event that m = 2 and / or n = 2, the same or different from one another. A1 and A2 are preferably each other different, especially when m and n each denote 1. A1 and A2 are preferred Phe, Cy or Dio, also Pyr or Pip; preferably contain the compounds of Formula I no more than one of the radicals Dio, Pyr, Pyn, Dit, Bi or Pip. aside from that compounds are preferred which have no more than three ring groups (A1 + A2) in the molecule contain.

If A1 and / or A2 and / or A3 is a 1,4-cyclohexylene group, then the 1,4-substituents can be arranged in the cis or trans position. There are those Preferred stereoisomers are those in which the groups R1- and - (A¹) m-1-Z- (A²) n-R² or R² - and - (A²) n-1-Z (A¹) m-R¹ are trans to one another.

Z has the general meaning - (CH2) s-Z²- (CH2) t-, where s + t die Can take values 0, 1, 2, 3 or 4; where the values are 0, 1 or 2 for s + t preferred, thus the structures -Z2 -, -CH2-Z2-, -Z2-CH2 -, -CH2-Z²-CH2-, - (CH2) 2-Z²-, -Z2- (CH2) 2-, but especially -Z2 -, -CH2-Z2-, -Z²-CH2- or -CH2-Z2-CH2- (Sub-formulas Ia to Id).

Z2 can assume the meanings mentioned, preferably SO, -SO2-, -SO2-O- and -SO2-S-, but especially -SO- and -SO2-.

In the compounds of the formulas above and below, R1 denotes and R2 is preferably alkyl, alkoxy or another oxaalkyl group, also H, CN, C1, F or Br. Alkyl, H, CN, C1 or F are particularly preferred. Farther compounds in which R1 and R2 are different from one another are preferred.

If R¹ and / or R² are alkyl radicals in which also one or two CH2 groups that are not adjacent can be replaced by O atoms, so they can be straight-chain or be branched. Preferably they are straight chain and have 2-8, in particular 3 - 7 carbon atoms.

Compounds of the formula I with branched wing groups R1, R2 and If they are optically active, R3 are important as chiral dopants. Branched Groups of this type usually contain no more than one chain branch. Preferred branched radicals R1, R2 and R3 are isopropyl, 2-butyl (= 1-methylpropyl), Isobutyl (= 2-methylpropyl), 2-methylpentyl, 3-methylpentyl, 2-methylbutyl, isopentyl (= 3-methylbutyl), isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy and 3-methylpentoxy. For compounds with branched wing groups R1 or R2 includes formula I both the optical antipodes and racemates as well their mixtures.

In the radicals R and R4, the alkyl groups preferably have 1 to 8, preferably 1-6 (for R) or 1-3 (for R4) carbon atoms and are preferably straight-chain.

The compounds of the formula I are made according to methods known per se 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, under reaction conditions that are known and known for the reactions mentioned are suitable. It is also possible to use what is known per se but is not mentioned here in more detail Make use of variants.

The person skilled in the art can use routine methods to use appropriate synthesis methods from the prior art (e.g. DE-OS 23 44 732, 24 50 088, 24 29 093, 25 02 904, 26 36 684, 27 01 591 and 27 52 975 relate to compounds with 1,4-cyclohexylene and 1,4-phenylene groups; DE-PS 26 41 724 relating to compounds with pyrimidine-2,5-diyl groups; DE-OS 32 28 350 relating to compounds with pyridazine-3,6-diyl groups; JP-OS 58-43 961 relating to compounds with pyrazine-2, 5-diyl groups; DE-OS 29 44 905 and 32 27,916 relating to compounds having 1,3-dioxane-2,5-diyl groups; DD 160 061 concerning Compounds with 1, 3-dithiane-2, 5-diyl groups; Regarding U.S. 4,261,652 and 4,219,265 Compounds having 1,4-bicyclo (2,2,2) octylene groups; DE-OS 31 50 312 pertaining to Compounds having decahydronaphthalene-2,6-diyl groups; DE-OS 29 49 080 concerning Compounds having 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups; and DE-OS 32 01 721 regarding connections with -CH2CH2 bridges).

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

The sulfoxides of formula I (where Z2 is -SO-) can be prepared by the corresponding thioethers, which are derived from the formula I, carefully oxidized according to methods and reaction conditions known per se. as Oxidizing agents can in principle serve all such compounds that have a corresponding have great redox potential. For example, the corresponding thioethers are oxidized with hydrogen peroxide, peracid, Cr (VI) compounds such as chromic acid, nitric acid, nitrous gases, N2O3, halogens such as chlorine, hypochlorites, KMnO4, N-bromosuccinimide, l-chlorobenzotriazole, Ce (IV) compounds such as (NH4) 2Ce (NO3) 6 negatively substituted aromatic diazonium salts such as o- or p-nitrophenyldiazonium chloride or else electrolytically under relatively mild conditions and at relatively low ones Temperatures (around -80 to +1000).

Hydrogen peroxide (in a 10 to 30% solution) is particularly suitable. The reaction takes place in organic solvents, which are usually miscible with water such as acetic acid, acetone or ethanol.

In particular, glacial acetic acid but also acetone are used here. The oxidation can also be carried out with percarboxylic acids (such as peracetic acid or chloroperbenzoic acid) as well as with concentrated or dilute nitric acid. All Forms of representation have in common that they are at relatively low temperatures, in the Usually carried out between -40 OC and +40 OC, preferably between -10 OC and 0 OC should be in order to exclude further oxidation of the sulfoxides formed. Under the conditions mentioned, the others, by definition possible, become functional Groups not attacked. The starting materials used are thioethers partly known from DOS 30 40 632, partly they can be analogous to known ones Connections according to standard procedures of the synthetic organic Chemistry are produced.

As a rule, corresponding halides are used with corresponding Mercaptans or thiophenols (the latter can be obtained by reducing the corresponding Sulphochlorides or the addition of corresponding phenols with dimethylthionocarbamoyl chloride and subsequent isomerization and hydrolysis) among those for this type of reaction usual conditions implemented.

Sulphoxides of the formula I can also be obtained by the action of appropriate organometallic compounds, preferably Grignard compounds, to appropriate Sulfinic acids or sulfinic acid esters are obtained in good yields, the organometallic compounds are produced according to known regulations and the reaction takes place even under normal conditions. The corresponding as starting compounds Serving sulfinic acids are usually obtained by reducing the corresponding sulfochlorides with metals such as

Zn, Fe and Mg or with lithium aluminum hydride among those known per se Conditions shown.

The preparation of the sulfones of the formula I (where z2 ~ SO2 ~ means) can in principle be achieved by means of methods that are used to represent well-known Sulphones already find general use. The manufacturing methods are particularly preferred the sulfones of the formula I from the corresponding thioethers by oxidation corresponding sulfinic acids with corresponding halides and from corresponding Sulfonic acids or their reactive derivatives.

The oxidation of thioethers on which the formula I is based must be carried out under comparatively somewhat more drastic conditions in order to achieve the Eliminate sulfoxide formation as far as possible. Usually they are suitable same Oxidizing agents used for the production of sulfoxides described above Find. Suitable solvents are, for example, water, aqueous mineral acids, aqueous alkaline solutions, lower alcohols such as methanol or ethanol, esters such as Ethyl acetate, ketones such as acetone, lower carboxylic acids such as acetic acid, nitriles such as Acetonitrile, hydrocarbons such as benzene, chlorinated hydrocarbons such as chloroform or CCl4.

The reaction temperatures are, however, significantly higher, namely between 20 and 120 OC, preferably between 30 and 70 OC. In addition, there is an excess of the Oxidizing agent advantageous. Potassium permanganate (1 to 10 % solution in glacial acetic acid or glacial acetic acid / carbon tetrachloride).

Furthermore, sulfones of the formula I can be obtained from the corresponding Sulphinic acids (the production of which has been described above) or sulphinates (e.g. from Sulfinic acids and alkali metal carbonate) and the corresponding halides. Ethanol or aqueous solutions thereof, but also other solvents, are used as solvents used. The reaction temperature depends on the boiling point of the solvent, but is preferably between 70 and 100 ° C.

In the preparation of sulfones of the formula I from sulfonic acid or their reactive derivatives are either corresponding sulfohalides, preferably sulfochlorides, with corresponding Grignard compounds among themselves known conditions, or possibly

the corresponding sulfohalides with the corresponding aryl hydrocarbons (R¹- (A¹) m-H or R²- (A²) n-H, where A¹ or A² is 1,4-phenylene) under catalytic Effect of aluminum chloride reacted.

Benzene is the preferred solvent, as well as others organic solvents are suitable. the Reaction temperatures are usually between 50 and 100 cc, preferably between 70 and 90 OC. The corresponding free sulfonic acids can optionally also be mixed with the corresponding Aryl hydrocarbons (Rl- (Al) m-H or R2- (A2) n-H, in which A1 or A2 1,4-phenylene means) under the action of dehydrating agents such as H2SO4 or P205 be implemented at 100 - 180 cc.

For the preparation of disulfones of the formula I (where z2 is -SO2SO2-) it is preferred to use corresponding sulfonic acid halides, preferably sulfochlorides, with corresponding sulfinates under conditions known per se for such reactions to, or one reduces suitable mixtures of corresponding sulfonic acid halides, preferably sulfochlorides, with sodium or potassium also reducing agents acting analogously at temperatures between 0 and 35 ° C., or suitable mixtures are oxidized corresponding sulfinic acids between 0 and 35 cc with potassium permanganate (e.g. 1- up to 10% solution in glacial acetic acid) or similarly acting oxidizing agents.

A common way of making sulfonic acid esters of the formula I (where Z2 is -SO2O-) to produce consists in the corresponding sulfonic acid halides, preferably sulfonic acid chlorides with appropriate alcohols preferably in ether or pyridine between 0 and 150 ° C, preferably between 20 and 100 cc to react. With an excess Good yields of alcohol can be achieved in this way. Furthermore, in known Way from corresponding sulfonic acid halides, preferably sulfochlorides, through Alkylation with corresponding diazo compounds sulfonic acid esters of the formula I prepared will.

Thiosulfonic acid of the formula I (in which z2 is -SO2S-) can be also produce according to methods known in principle. This is how, for example, corresponding symmetrical or asymmetrical disulfides (can be produced by careful Oxidation of corresponding mercaptans) with suitable, used with a slight excess Oxidizing agents, preferably 0-25 OC, to oxidize the desired compounds. By reacting corresponding sulfenyl halides, preferably sulfenyl chlorides (can be produced e.g. by halogenation of appropriate mercaptans), with appropriate Thiosulfonic acid esters of the formula I can also be sulfinates in good yields getting produced.

Thiosulfonic acid esters of the formula I (in which z2 is -SO2S-) can also be produced by methods known in principle. This is how, for example, corresponding symmetrical or asymmetrical disulfides (can be produced by careful Oxidation of corresponding mercaptans) with suitable, used with a slight excess Oxidizing agent, preferably hydrogen peroxide at low temperatures, preferably 0 - 25 OC to oxidize to the desired compounds. By implementing appropriate Sulfenyl halides, preferably sulfenyl chlorides (can be prepared e.g. by halogenation corresponding mercaptans), with corresponding sulfinates, thiosulfonic acid esters can also be used of formula I can be prepared in good yields.

Sulphonamides of the formula I (in which z2 -SONR4 ~ and R4 H or alkyl with mean one to 5 carbon atoms) can be essentially by almost all methods, commonly known for sulfonamides.

The conversion of corresponding sulfonic acids is preferred or their reactive derivatives (e.g.

Sulfonic acid halides) with corresponding primary or secondary Amines of the structure HNR4- (CH2) (A2) n-R2 or HNR4- (CH2) 5 (A1)) m-R¹ (with the given Meanings for A, R-, R, R, s, t, m and n) in alkaline, neutral or weak acidic aqueous or organic medium, preferably in an aqueous-ethanolic solution with acetate, carbonate or pyridine, at temperatures between 0 and 120 ° C., preferably 40 - 80 OC. The reaction takes place in a strongly alkaline solution due to the formation of sulfimides with lower yields. Also the N-alkylation of corresponding sulfonamides of the structure R¹, 2-Am-n1,2- (CH2) s'tSO2NHR4 with corresponding halides of the structure R-A- (CH2) S t-Hal (with the meanings given) in an alkaline medium at temperatures between 50 and 150 ° C is a common way to prepare sulfonamides of the formula I.

The compounds of formula I can also be prepared in the manner be by adding a compound that otherwise corresponds to formula I, but in place of H atoms one or more reducible groups and / or C-C double or triple bonds contains, reduced.

Preferred reducible groups are carbonyl groups, in particular keto groups, also, for example, free or esterified hydroxyl groups or aromatically bound halogen atoms. Preferred starting materials for the reduction correspond of the formula I, but can instead of a cyclohexane ring a cyclohexene ring or Cyclohexanone ring and / or instead of a -CH2CH2 group a -CH = CH group and / or instead of a -CH2 group a -CO group and / or instead of an H atom a free or functionally modified (e.g. in the form of its p-toluenesulfonate) Contain OH group.

The reduction can take place, for example, by catalytic hydrogenation Temperatures between about 0 ° and about 200 ° as well as printing between about 1 and 200 bar in an inert solvent, e.g. an alcohol such as methanol, Ethanol or isopropanol, an ether such as tetrahydrofuran (THF) or dioxane, a Esters such as ethyl acetate, a carboxylic acid such as acetic acid or a hydrocarbon like cyclohexane. Suitable catalysts are suitable noble metals such as Pt or Pd, which is in the form of oxides (e.g. PtO2, PdO), on a carrier (e.g. Pd on carbon, Calcium carbonate or strontium carbonate) or in finely divided form can.

Ketones can also be made according to Clemmensen's methods (with zinc, amalgamated Zinc or tin and hydrochloric acid, expediently in aqueous-alcoholic solution or in heterogeneous phase with water / toluene at temperatures between about 80 and 120 0) or Wolff-Kishner (with hydrazine, expediently 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 0) to the corresponding compounds of the formula I, which contain alkyl groups and / or -CH2CH2 bridges, are reduced.

Reductions of suitable compounds of the formula I with complex hydrides such as LiAlH4 or NaBH4 are only possible if there are possible functional sulfur groups, e.g. arylsulfonyloxy groups are not attacked reductively.

Compounds of the formula I are still available by calling on a corresponding cyclohexene derivative (which corresponds to formula I, but instead of of the radical A1 and / or A2 and / or A3 contains a 1-cyclohexene-1,4-diyl group, which can carry 1 or 2 F, Cl or Br atoms and / or CN groups) a compound the formula HX (fluorine, chlorine, bromine or hydrogen cyanide) attaches.

This addition works, for example, in the presence of an inert solvent, e.g. a halogenated hydrocarbon such as CH2C12 or CHC13, a nitrile such as acetonitrile or an amide such as dimethylformamide (DMF) at temperatures between about -10 and +150 ° and pressures between about 1 and 100 bar. An addition of catalysts can be beneficial, e.g. HCN addition can be achieved by adding palladium-bis- [2,3, -O-isopropylidene-2,3-dihydroxy-1,4-bis- (diphenylphosphino) -butane] be catalyzed.

Esters of the formula I (R1 and / or R2 and / or R3 = -O-COR and / or -COOR) can also be obtained by esterifying corresponding carboxylic acids, e.g. of the formulas R-COOH, R1- (A1) m -Z- (A2) n -COOH, R2- (A2) n -Z- (A1) m -COOH, R1- (A1) m -Z- (A2) m -Z1-A3-COOH (or their reactive derivatives) with alcohols or phenols of the formulas R¹- (A¹) m-Z- (A²) n-OH, R²- (A²) n -Z- (A¹) m-OH or R1- (A¹) m -Z- (A²) n -Z¹-A3-OH (or their reactive Derivatives).

Suitable reactive derivatives of the carboxylic acids mentioned are in particular the acid halides, especially the chlorides and bromides, and also the Anhydrides, e.g.

also mixed anhydrides, azides and esters, especially alkyl esters with 1 - 4 carbon atoms in the alkyl group.

As reactive derivatives of the alcohols mentioned or

Phenols come in particular the corresponding metal alcoholates or Phenolates of the formulas R1- (A1) m -Z- (A2) n OM, R2- (A2) n -Z- (A1) m-OM, R1- (A1) m -Z- (A2) n -Z1-A3-OM or R²- (A²) n-Z- (A¹) m-Z¹-A³ -OM, wherein M is one equivalent of a metal, preferably an alkali metal such as Na or K.

The esterification is advantageous in the presence of an inert solvent carried out. 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 such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfolane. Solvents immiscible with water can also be advantageous for the azeotropic distillation of the esterification formed water can be used. Occasionally there can also be an excess of one organic base, e.g. pyridine, quinoline or triethylamine as a solvent for the esterification can be applied. The esterification can also take place in the absence of a Solvent, e.g. by simply heating the components in the presence of sodium acetate, be performed. The reaction temperature is usually between -50 ° and +250 °, preferably between -20 ° and +80 °. At these temperatures are the Esterification reactions usually ended after 15 minutes to 48 hours.

In detail, the reaction conditions for the esterification largely depend on the nature of the raw materials used. So it becomes 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. One the preferred mode of reaction is the conversion of an acid anhydride or in particular of an acid chloride with an alcohol, preferably in a basic medium, wherein as bases in particular alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates 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 of importance. One Another preferred embodiment of the esterification is that the alcohol respectively.

the phenol first into the sodium or potassium alcoholate or phenolate transferred, e.g. by treatment with ethanolic sodium or potassium hydroxide solution, this isolated and mixed with sodium hydrogen carbonate or potassium carbonate with stirring suspended in acetone or diethyl ether and this suspension with a solution of the Acid chloride or anhydride mixed in diethyl ether, acetone or DMF, appropriate at temperatures between about -25 ° and +20 °.

Dioxane derivatives of the formula I (in which one of the groups A1 and / or A2 and / or A3 is a 1,3-dioxane-2,5-diyl group) are expediently by reaction a corresponding aldehyde, e.g. of the formulas R1- (A1) -Z- (A2) n 1-CHO, R2- (A2) n-Z-CHO or R1-CH = O (or one of its reactive derivatives) with a corresponding one 1,3-Diol e.g. of the formulas R²- (A²) n-1-CH (CH2OH) 2, R1- (A1) m ~ Z ~ (A) n ~ 1-CH (CH2OH) 2 or R1n-1- (A1) m-Z-CH (CH2OH) 2 (or one of its reactive derivatives) produced, preferably in the presence of an inert solvent such as benzene or toluene and / or a catalyst, e.g. a strong acid such as sulfuric acid, benzene or p-toluenesulphonic acid, at temperatures between about 20 ° and about 150 °, preferably between 80 ° and 120 °. As reactive derivatives of the starting materials are primarily suitable corresponding acetals.

The aldehydes and 1,3-diols mentioned and their reactive derivatives are partly known, partly they can be carried out without difficulty using standard procedures organic chemistry from compounds known from the literature. For example are the aldehydes by oxidation of corresponding alcohols or by reduction of the corresponding Carboxylic acids or their derivatives, the diols by reducing the corresponding diesters available.

For the preparation of nitriles of the formula I (in which R1 and / or R2 are CN and / or where A and / or A1 and / or A2 and / or A3 are replaced by at least one CN group is substituted) corresponding acid amides, e.g.

those in which there is a CONH2 group in place of the radical X are dehydrated will. The amides are e.g. made from corresponding esters or acid halides Reaction with ammonia available. Examples of suitable dehydrating agents are inorganic acid chlorides such as SOCl2, Pol3, Pol5, POCl3, SO2Cl2, COC12, also P205, P2S5, AlCl3 (e.g. as a double compound with NaCl), aromatic sulfonic acids and sulfonic acid halides. You can do this in the presence or absence of an inert solvent at temperatures operate between about 0 ° and 150 °; as solvents e.g.

Bases such as pyridine or triethylamine, aromatic hydrocarbons such as benzene, toluene or xylene or amides such as DMF into consideration.

For the preparation of the aforementioned nitriles of the formula I can the corresponding acid halides, preferably the chlorides, are also reacted with sulfamide, expediently in an inert solvent such as tetramethylene sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °. After the usual work-up you can isolate the nitriles directly.

Nitrilles of the formula I, in which A¹ and / or A² and / or A³ are aromatic Mean ring groups can also be produced in the manner known per se, by corresponding aryl halides with anhydrous cyanides, especially copper-I-cyanide in pyridine, dimethylformamide, methylpyrrolidone, quinoline or adequate solvents at temperatures between 80-220 OC, preferably between 100-205 OC.

Nitriles of the formula I in which R1 and / or R2 and / or R3 denotes CN and A1 and / or A2 and / or A3 are not aromatic, can be selected from corresponding Alkyl halides with cyanides, such as NaCN or KCN, in dilute alcoholic solution, in dimethyl sulfoxide or in suitable higher boiling solvents at temperatures preferably between 50 and 170 OC can be obtained.

The corresponding alkyl or aryl halides can be found in the standard procedures described in the literature.

Ethers of the formula I (in which R1 and / or R2 and / or R3 are an alkyl group means in which one or two non-adjacent CH2 groups are replaced by O atoms are are obtained by etherification of corresponding hydroxy compounds, preferably corresponding Phenols, available, the hydroxy compound expediently initially in a corresponding Metal derivative, e.g. by treatment with NaH, NaNH2, NaOH, KOH, Na2CO3 or K2CO3 converted into the corresponding alkali metal alcoholate or alkali metal phenate will. This can then with the corresponding alkyl halide, sulfonate or dialkyl sulfate are reacted, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.

For the preparation of compounds of the formula I in which R1 and / or R2 and / or R3 means SOR or SO2R, in principle all those processes can be used which have already been detailed above in the description of the groups Z and Z2 according to the invention have been described.

A base of the formula I can be converted into the associated acid addition salts with an acid be transferred. Inorganic acids can be used for this reaction, e.g. sulfuric acid, nitric acid, hydrohalic acids such as hydrochloric acid or hydrobromic acid, phosphoric acids such as orthophosphoric acid, sulfamic acid, also organic acid, especially aliphatic, alicyclic, araliphatic, aromatic or heterocyclic monobasic or polybasic carboxylic, sulfonic or sulfuric acids, e.g. formic acid, acetic acid, propionic acid, pivalic acid, diethylene acetic acid, malonic acid, Succinic acid, pimelic acid, fumaric acid, maleic acid, lactic acid, tartaric acid, malic acid, Benzoic acid, salicylic acid, 2- or 3-phenylpropionic acid, citric acid, gluconic acid, Ascorbic acid, nicotinic acid, isonicotinic acid, methane or ethanesulphonic acid, ethanedisulphonic acid, 2-hydroxyethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalene-mon- and disulfonic acids, laurylsulfuric acid.

Conversely, it is possible to make a compound from an acid addition salt of the formula I to release the base of the formula I by treatment with a base, e.g. with a strong inorganic base such as KOH or NaOH.

The liquid-crystalline phases according to the invention consist of 2 to 15, preferably 3 to 12 components, including at least one compound of Formula I.

The other components are preferably selected from the nematic ones or nematogenic substances, in particular the known substances from the classes the azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, Cyclohexanecarboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, Cyclohexylcyclohexane, cyclohexylnaphthalenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, Phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolanes and substituted cinnamic acids.

The most important as components of such liquid-crystalline phases Compounds in question can be characterized by the formula II, R'-L-G-E-R "II where L and E are each a carbo- or heterocyclic ring system that of 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted Biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2, 5-disubstituted Pyrimidine and 1,3-dioxane rings 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, Quinazoline and tetrahydroquinazoline formed group, G -CH = CH - CH = CY- -CH = N (O) - CC- ~ CH2 - CH2 - CO-O- -CH2-O - CO-S- -CH2-S - CH = N- -COO-Phe-COO- or a single bond, Y halogen, preferably chlorine, or -CN, and R 'and R "alkyl, Alkoxy, alkanoyloxy or alkoxycarbonyloxy with up to 18, preferably up to 8 Carbon atoms, or one of these radicals also CN, NC, NO2, CF3, F, C1 or Br mean.

In most of these compounds, R 'and R "are different from one another, one of these radicals is usually an alkyl or alkoxy group. But others too Variants of the intended substituents are common. Lots of such substances or mixtures thereof are available commercially. All of these substances are after methods known from the literature are available.

The phases according to the invention contain about 0.1 to 100, preferably 10 to 100%, one or more compounds of the formula I. Also preferred are liquid-crystalline phases according to the invention, containing 0.1-40, preferably 0.5-30% of one or more compounds of formula 1.

The phases according to the invention are produced in a manner that is conventional per se Way. As a rule, the components are dissolved in one another, expediently in the case of increased Temperature.

The liquid-crystalline phases can be increased by suitable additives of the invention are modified so that they are in all previously known Types of liquid crystal display elements can be used.

Such additives are known to the person skilled in the art and are detailed in the literature described. For example, electrolyte salts, preferably ethyl dimethyl dodecyl ammonium 4-hexyloxybenzoate, Tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf. e.g. I. Haller et al., Mol.Cryst.Lig.Cryst. Volume 24, pages 249-258 1973)) to improve conductivity, dichroic dyes for the production of colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases can be added. Such substances are e.g. in DE-OS 22 09 127, 22 40 864, 23 21 632, 23 38 281, 2450 088, 26 37 430, 28 53 728 and 29 02 177 described.

The following examples are intended to illustrate the invention without limiting it limit.

Example 1 4.7 g of 4- <trans-4-n-propylcyclohexyl) thiophenol (can be prepared from the corresponding phenol by reaction with dimethylthiocarbamoyl chloride, Rearrangement of the thione carbamate to the thiol carbamate and then saponification), 5 g (trans-4-n-pentylcyclohexyl) bromomethane and 2.8 g potassium carbonate in 30 ml dimethylformamide are heated to 900 for 5 hours while stirring. The salt is filtered off and concentrated Half of the filtrate is added, water is added and the mixture is extracted with dichloromethane.

The combined extracts are washed with water over sodium sulfate dried and the solvent was distilled off. The residue is recrystallized from ethanol.

Yield 6.1g.

Dissolve the sulfide in 30 ml of chloroform and drop at 5-100 one Solution of 11.25 g of 3-chloroperbenzoic acid (70%) in 200 ml of chloroform. After this Standing overnight at room temperature is washed successively with sodium carbonate, Sodium sulfite solution and water, dried over sodium sulfate, the solvent distilled and the 4- (trans-4-n-PropylcycloheXyl) - [(trans-4-n-pentylcyclohexyl) -methylsulfonyl] -benzene crystallizes from methanol.

Example 2 Analogously to Example 1, 4-n-heptyl - [(trans-4-n-pentylcyclohexyl ) methylmercapto] benzene (melting point 380) by oxidation with 3-chloroperbenzoic acid 4-n-Heptyl - [(trans -4-n -pentylcyclohexyl) methylsulfonyl] benzene.

Example 3 4.9 g of 2 - [(trans -4- n -pentylcyclohexyl) methylmercapto] -4-chloro-5- (4-n-hexyloxyphenyl) pyrimidine (represented by the conversion of the ethyl ester from the condensation of α-hydroxymethylene-4-n-hexyloxyphenylacetic acid hydroxy compound obtained with (trans-4-n-pentylcyclohexyl) methylisothiuronium bromide with phosphorus oxychloride / N, N-diethylaniline) and 3.3 g zinc powder in 40 ml ethanol are refluxed for one hour after adding 2 ml of glacial acetic acid.

After working up, 2.27 g of the dehalogenated compound are obtained, by oxidation with 1.12 g of 85% 3-chloroperbenzoic acid in 30 ml of dichloromethane into the (trans-4-n-Pentylcyclohexyl) -methyl- [5- (4-n-HeXyloxyphenyl) -pyrimidin-2-yl] sulfoxide is transferred.

Example 4 4.3 g of 4-n-heptylcyclohexanethiol (obtained by Conversion of 4-n-heptylcyclohexyl bromide with potassium O-ethylxanthogenate and saponification of the reaction product), 6 g of trans, trans-4-bromomethyl-4'-n-propylbicyclohexyl and 100 ml of 0.2 N ethanolic potassium hydroxide solution under reflux for two hours, then distilled Most of the alcohol is removed, the residue is mixed with water and extracted with ether. The extracts are washed neutral with dilute sodium hydroxide solution and water, dried and the solvent removed.

The residue becomes via the thiourea inclusion compound and subsequent recrystallization of the pure trans, trans-4 (4-trans-4-n-heptylcyclohexyl) mercaptomethyl-4'-n-propylbicyclohexyl and the sulfoxide is obtained therefrom by oxidation analogously to Example 3.

Example 5 7.6 g of trans, trans-4- (4-n-pentylcyclohexyl) cyclohexanol and 8.25 g of 4-n-heptylbenzoesulfonic acid chloride are placed in 100 ml of dichloromethane and 5 ml of pyridine were added dropwise at 10-200. The mixture is allowed to come to room temperature and is stirred overnight after washing with dilute hydrochloric acid, 5% sodium hydrogen carbonate solution and Water neutral and dries over sodium sulfate. After distilling off the solvent 13.2 g of trans, trans-4- (4-n-pentylcyclohexyl) cyclohexyl- (4-n-heptylbenzoesulfonate) are obtained.

Example 6 In an analogous manner, from 4.1 g of 4-cyanothiophenol, 9.0 g of trans -4-n-Propylcyclohexylbenzolsul fochlorid (prepared by neutralizing the obtained from the reaction of trans-4-n-propylcyclohexylbenzene with chlorosulfonic acid Mixture of sulfonic acid and sulfochloride with sodium hydroxide solution and subsequent heating of the sodium salt with phosphorus oxychloride) 7.3 g of trans-4-n-propylcyclohexylbenzenethiosulfonic acid 5-cyanophenyl ester.

Example 7 To 5.9 g of 1-amino-2- [trans, trans-4- (4-n-heptylcyclohexyl) cyclohexyl] ethane (Can be prepared from trans, trans -4- (4-n-heptylcyclohexyl) -hydroxymethylcyclohexane by conversion into the tosylate, reaction of the same with potassium cyanide in dimethylformamide and reduction of the nitrile thus obtained with lithium malanate), dissolved in 40 ml of dry Pyridine are added dropwise at 0-50 3.0 g of 4-ethoxybenzenesulphonyl chloride. One lets React for one hour, pour onto ice and extract with dichloromethane. The United Extracts are made with dilute hydrochloric acid, 5% sodium hydrogen carbanate solution and Washed neutral with water and dried over sodium sulfate.

After distilling off the solvent and recrystallization of the A residue from ethanol gives 5.4 g of 1- (4-ethoxybenzenesulfonamido) -2- [trans, trans-4- (4-n-heptylcyclohexyl) cyclohexyl] ethane.

Claims (6)

Claims 1. Compounds of the formula I R¹- (A¹) m-Z- (A²) n-R² in which R1 and R2 are each H, an alkyl group having 1 to 10 carbon atoms, in which also a or two non-adjacent CH2 groups can be replaced by O atoms, -C00R, -0C0R, F, C1, Br, CN, SR, SOR, SO2R or R³-A³-Z¹-, where only R1 or R2 is H or R3-A3 -Z1-may be, R is an alkyl group with 1 - 10 carbon atoms A¹, A², A³ each unsubstituted or by one or two F and / or Cl atoms and / or Br atoms and / or CH3 groups and / or CN groups-substituted 1,4-phenylene groups, in which optionally a or two = CH groups can be replaced by = N-, 1,4-cyclohexylene groups, in which optionally one or two non-adjacent CH2 groups can be replaced by 0 can, 1,3-dithiane-2,5-diyl, piperidine-1,4-diyl or 1,4-bicyclo (2,2,2) octylene groups, Z (CH2) s-Z²- (CH2) t, zl -COO-, -O-CO-, -CH2-CH2-, -OCH2-, 2 Z or a single bond, Z² -SO-, -SO2-, -SO2-SO2-SO2-, -SO2-O-, -SO2S-, -SO2NR4-, R3 H, an alkyl group with 1-10 carbon atoms, in which one or two non-adjacent CH2 groups can be replaced by O atoms, F, C1, Br, CN, -COOR, -OCOR, SR, SOR or SO2R R4 H or alkyl group with 1 - 5 carbon atoms, m and n each 1 or 2, where for m = 2 and / or n = 2, the groups A1 and / or A2 are identical to or from one another may be different, s and t each 0, 1 or 2 2. Method of manufacture of compounds of the formula I according to claim 1, characterized in that for Preparation of sulfoxides of the formula I (in which Z² and / or R¹ and / or R² and / or R³ mean -SO-), oxidized the corresponding thioethers, or that one for the production of sulfones of the formula I (in which z2 and / or R1 and / or R2 and / or R3 are -S02-), the corresponding thioethers are oxidized or the corresponding sulfonic acids or one of their reactive derivatives with organometallic compounds or optionally with corresponding aryl hydrocarbons or corresponding sulfinates with halides to react, or that one for the preparation of disulfones of the formula I (in which z2 is - (SO2) 2), the corresponding sulfinic acids are oxidized or the corresponding sulfonyl halides with the corresponding sulfinates or with alkali metal, or that one for the preparation of sulfonic acid esters of Formula I (in which Z2 is 5020) the corresponding sulfonic acids or one of them reactive derivatives with the corresponding alcohols or their reactive derivatives Implements derivatives, or that one for the production of thiosulfonic acid esters of the formula I (in which z2 is SO2S-) oxidizes the corresponding disulfides or reacts the corresponding sulfenyl halides with the corresponding sulfinates, or that for the preparation of sulfonamides of the formula (in which Z² is SO2NR4- and R4 has the meaning given), the corresponding sulfonic acids or one Reacts their reactive derivatives with corresponding amines or corresponding Sulphonamides of the formula R ° -SO2 NHR4 (in which R0 is R¹- (A¹) m- (CH2) s- or R²- (A²) n- (CH2) t- and R¹, R², A¹, A², n, m, s and t have the meanings given), with a converting the corresponding halide, or that one is a compound which is otherwise of the formula I corresponds, but instead of H atoms one or more reducible groups and / or contains C-C double or triple bonds, with a suitable reducing agent Treated agent, or that for the preparation of esters of the formula I (wherein R¹ and / or R² and / or R³ is -OCOR and / or -COOR and / or Z¹ is -COO- or -OCO- means) a corresponding carboxylic acid or one of its reactive derivatives with a corresponding alcohol or one of its reactive derivatives, or that for the preparation of ethers of the formula I (in which R1 and / or R2 and / or R3 denotes an alkyl group in which one or two non-adjacent CH2 atoms are replaced by 0) etherifies a corresponding hydroxy compound, or that one for the preparation of dioxane derivatives of the formula I (in which A1 and / or A2 and / or A3 signify 1,3-dioxane-2,5-diyl) a corresponding aldehyde with a corresponding one Converts diol, or that one for the preparation of nitriles of the formula I (where R1 and / or R2 and / or R3 are CN, and / or where A1 and / or A2 and / or A3 is substituted by at least one CN group) a corresponding carboxamide dehydrated or a corresponding carboxylic acid halide with sulfamide or a reacting corresponding halide with a cyanide, and / or that one optionally a base of the formula I by treatment with an acid in one of its acid addition salts converts, or that you optionally a compound of formula I from one of its Acid addition salts liberated by treatment with a base. 3. Use of the compounds of the formula I according to claim 1 as components liquid crystalline phases. 4. Liquid-crystalline phase with at least two components, thereby characterized in that at least one component is a compound of the formula I according to Claim 1 is. 5. Liquid crystal display element, characterized in that there is a liquid-crystalline phase according to claim 4 contains. 6. Electro-optical display element according to claim 5, characterized in that that it contains a liquid-crystalline phase according to claim 4 as dielectric.