DD254590A5 - CHIRAL-TREATED SMEKTIC LIQUID CRYSTALLINE PHASE - Google Patents

Abstract

The present invention relates to a chiral tilted smectic liquid crystalline phase having at least two liquid crystalline components, characterized in that it contains at least one optically active compound of the formula I R1 -Q1-CHX-Q2-A4-Z1-A2 (Z2-A3) n-R2 Ienthaelt. With the provision of the compounds of the formula I, the range of liquid-crystalline substances which are suitable for producing ferroelectric mixtures under various aspects of application technology is also very broadly broadened.

Description

Field of application of the invention

The invention relates to a chiral tilted smectic liquid-crystalline phase having at least two liquid-crystalline components, characterized in that it contains at least one optically active compound of the formula I.

, R ^l -Q ¹ -C * HX-Q ² -A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -R ² I

R ¹ and R ² each represent a straight-chain or branched alkyl or perfluoroalkyl group each having 1-12 C atoms, in which also one or more CH ₂ or CF ₂ groups is represented by a grouping selected from the group -O-, -S-, -CO-, 0-C0-, -O-COO-, -CO-, -CH = CH-, -CHHalogen- and -CHCN- or may also be replaced by a combination of two suitable moieties, wherein 'two heteroatoms are not directly linked to each other, one of the groups R ¹ and R ^{2 is} also F, Cl, Br or CN and R ^{2 is} also H,

A ² , A ³ and A ^{4 are} each unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups substituted 1,4-phenylene, wherein also one or two CH- May be replaced by N, 1,4-cyclohexylene, wherein also one or two non-adjacent CH ₂ groups may be replaced by O atoms and / or S atoms, piperidine-1,4-diyl, 1,4- Bicyclo (2,2,2) -octylene, naphthalene-2,6-diyl, decyhydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups,

Z ¹ and Z ² are each -CO-O-, -0-CO -, - CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -C≡C- or a single bond, X is halogen, CN or CH ₃ , nOoderi,

Q ¹ denotes a single bond or alkylene having 1 to 3 C atoms, in which also a CH ₂ group is represented by -O-, -CO-, -O-CO-, -CO-O-, -CH = CH-COO-, -CH = CH-, -CHHalogen- and / or -CHCN- may be replaced, and Q ² alkylene having 1 to 6 C atoms, wherein also one or two CH ₂ groups by -0-, -CO-, - O-CO-, -CO-O, -CH = CH-COO-, -CH = CH-, -CHHalogen and / or -CHCN- may be replaced, wherein two heteroatoms are not directly linked together, or a single bond means with the provisos that

(a) R ¹ - ^ ² - is a group having at least one branch, and

(b) X is CH ₃ and / or R ¹ -Q ² - is a group having at least two branches if -A ⁴ -Z ¹ -A ² -R ² 4'-alkoxybiphenyl-4-yl and Q ² -CO -O-means

contains.

Characteristic of the known technical solutions

Like similar compounds described in DE-OS 3515373, the compounds of the formula I can be used as components of chiral tilted smectic liquid-crystalline phases.

, Chiral-tutted smectic liquid-crystalline phases with ferroelectric properties can be prepared by mixing base mixtures with one or more tinted smectic phases with a suitable chiral dopant (L A. Beresnev et al., Mol. Cryst. Liq. Cryst. 89, 327 [1982] HR Brand et al., J. Physique 44, [lett], L-771 [1983]). Such phases can be used as dielectrics for fast switching displays based on the principle of SSFLC technology described by Clark and Lagerwall (Naclark and ST Lagerwall, Appl. Phys. Lett., 36, 899 [1980], USP 4,367,924) based on the ferroelectric properties of the chiral tilted phase are based. In this phase, the elongated molecules are arranged in layers, the molecules having a tilt angle to the layer normal. As layer to layer progresses, the direction of tilt changes by a small angle with respect to an axis normal to the layers so that a helical structure is formed. In displays based on the principle of SSFLC technology, the smectic layers are arranged perpendicular to the plates of the cell. The helical arrangement of the valve directions of the molecules is suppressed by a very small distance of the plates (about 1-2μ.ιη). This forces the longitudinal axes of the molecules to align in a plane parallel to the plates of the cell, giving rise to two excellent tilt orientations. By applying a suitable alternating electric field can be switched back and forth in the spontaneously polarizing liquid-crystalline phase between these two states. This switching process is significantly faster than conventional n-type liquid crystal (TN-LCD) based cells.

A major drawback to many applications of currently available materials with chiral tilted smectic phases (such as Sc *) is their relatively high optical anisotropy, which is due to relatively high viscosity values and / or re-low values for spontaneous polarization due to insufficiently short switching times and that the dielectric anisotropy has values greater than zero or, if negative, values only slightly different from zero. Negative values of dielectric anisotropy are required if the required planar orientation is effected by superposition of the drive field with a small amplitude AC holding field (J. M. Geary, SID Meeting, Orlando / Florida, April / May 1985, Lecture 8.3).

Object of the invention

The invention had the object of finding new compounds which are suitable as components of such phases.

Explanation of the essence of the invention

It has now been found that the use of compounds of the formula I as components of chiral tilted smectic mixtures can substantially reduce the disadvantages mentioned. The compounds of the formula I are therefore outstandingly suitable as components of chiral tilted smectic liquid-crystalline phases. In particular chemically stable chiral tilted smectic liquid-crystalline phases with favorable ferroelectric phase ranges, in particular with broad Sc * phase ranges, have a very favorable ratio of rotational viscosity to spontaneous polarization (γ / Ρ), negative or positive dielectric anisotropy, low optical anisotropy, favorable pitch height and for such phases high values for the spontaneous polarization and very short switching times can be produced. P is the spontaneous polarization in nC / cm ² .

With the provision of the compounds of the formula I, the range of liquid-crystalline substances which are suitable for producing ferroelectric mixtures under various aspects of application technology is also very broadly broadened.

The compounds of the formula I have a wide range of applications. Depending on the choice of substituents, these compounds may serve as base materials from which liquid crystalline phases are predominantly composed; However, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds, for example the dielectric and / or optical anisotropy and / or the spontaneous polarization and / or the phase region and / or the tilting effect and / or the pitch and / or the Switching times of such a phase vary. The compounds of the formula I are furthermore suitable as intermediates for the preparation of other substances which can be used as constituents of liquid-crystalline phases.

The compounds of the formula I are colorless in the pure state, have relatively low values of optical anisotropy and very favorable values for y / P. Some of the compounds of the formula I show liquid-crystalline mesophases in a temperature range which is favorably located for the electro-optical use, but it is also possible to use isotropic or monotropic liquid-crystalline compounds of the formula I as components of chiral tilted smectic phases. Chemically, thermally and against light, they are stable

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

The invention also relates to chiral tilted smectic liquid-crystalline phases containing at least one optically active compound of the formula I with at least one asymmetric carbon atom.

The invention further relates to liquid crystal display elements, in particular electro-optical display elements containing such phases.

For the sake of simplicity, in the following, Ph denotes a 1,4-phenylene group, in which also one or two CH groups can be replaced by N, Cy denotes a 1,4-cyclohexylene group, in which also one or two non-adjacent CH ₂ groups are replaced by O-- Atoms can be replaced and Bi a bicyclo (2,2,2) octylene group.

Above and below, R ¹ , R ² , n. A ² , A ³ , A ⁴ , Q ¹ , Q ² , X, Z ¹ and Z ^{2 have} the stated meaning, unless expressly stated otherwise. c * is an asymmetric carbon atom.

The compounds of the formula I accordingly comprise in particular compounds of the subformulae I a and I b (with two rings)

_R i_Qi_C * HX-Q ² -A ⁴ -A ² -R ² la

Ri_Qi_C * HX-Q ² -A ⁴ -z ¹ -A ² -R ² Ib

and Ic to If (with three rings):

Ri_Qi_C * HX-Q ² -A ⁴ -A ² -A ³ -R ² . ic

ri_qi_C * hx_Q ² _a ⁴ _A ² -Z ² -A ³ -R ² Id

Ri-Qi-C ^ HX-Q ^ -Z ^ -A ³ - « ² Ie

ri_qi_C * HX-Q ² -A ⁴ -Z ¹ -A ² -Z ² -A ³ -R ² If

Of these, those of the formulas Ia, Ib, Ic, Id and Ie are particularly preferred.

The preferred compounds of the formula Ia include those of the partial formulas Ia1 to Ia4:

Ri_Qi_C * HX-Q ² -Ph-Ph-R ² I a 1

Ri_Qi_C * HX-Q ² -Cy-Ph-R ² I a 2

Ri_Qi_C * HX-Q ² -Ph-Cy-R ² I a 3

Ri_Qi_C * HX-Q ² -Cy-Cy-R ² Ia4

Of these, those of the formulas Ia and Ia3 are particularly preferred.

The preferred compounds of the formula Ib include those of the partial formulas Ib1 to Ib4:

Ri_Qi_C * HX-Q ² -Ph-Z ¹ -Ph-R ² IbI

Ri_Qi_C * HX-Ü ² -Cy-Z ¹ -Ph-R ² Ib ²

Ri_Qi_C * HX-Q ² -Ph-Z ¹ -Cy-R ² I b 3

Ri_Qi_C * HX-Q ² -Cy-Z ¹ -Cy-R ² Ib 4

Of these, those of the formulas Ib1 and Ib3 are particularly preferred.

The preferred compounds of the formula Ic include those of the sub-formulas Ic 1 to Ic4:

Ri_Qi_C * HX-Q ² -Ph-Ph-Cy-R ² I c 1

R ¹ -Q ¹ -C * HX-Q ² -Ph-Cy-Cy-R ² I c 2

Ri_Qi_C * HX-Q ² -Ph-Cy-Ph-R ² Ic3

Ri_Qi_C * HX-Q ² -Ph-Ph-Ph-R ² Ic4

The preferred compounds of the formula Id include those of the partial formulas Id 1 to Id 3:

Ri_Qi_C * HX-Q ² -Ph-Ph-Z ² -Cy-R ² I d 1

Ri_Qi_C * HX-Q ² -Ph-Cy-Z ² -Ph-R ² 'I d 2

Ri_Qi_C * HX-Q ² -Ph-Ph-Z ² -Ph-R ² I d 3

The preferred compounds of the formula Ie include those of the subformulae I e 1 to Ie 5:

Ri_Qi_C * HX-Q ² -Ph-Z ¹ -Ph-Ph-R ² Ie1

Ri_Qi_C * HX-Q ² -Ph-Z ¹ -Ph-Cy-R ² Ie ²

R ¹ -Q ¹ -C * HX-Q ² -Ph-Z ¹ -Cy-Ph-R ² | _e 3

Ri_Qi_C * HX-Q ² -Ph-Z ¹ -Cy-Cy-R ² Ie 4

Ri_Qi_c * HX_Q ² -Cy-Z ¹ -Ph-Ph-R ² I e 5

Preference is given to compounds of the formulas above and below in which R ^{2 is} alkyl, -O-alkyl, -CO-alkyl, -CO-O-alkyl, -OCO-alkyl or -OCOO-alkyl.

In the preferred compounds of the formulas above and below, the alkyl radicals in which also a CH ₂ group (alkoxy or oxaalkyl) may be replaced by an O atom may be straight-chain or branched. They preferably have 5, 6, 7, 8, 9 or 10 carbon atoms and accordingly preferably represent pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentoxy, hexoxy, heptaxy, octoxy, nonoxy or decoxy, furthermore also ethyl, propyl , Butyl, undecyl, dodecyl, propoxy, ethoxy, butoxy, undecoxy, dodecoxy, 2-oxapropyl (= 2-methoxymethyl), 2 - (= ethoxymethyl) or 3-oxabutyl (= 2-methoxypentyl), 2-, 3- or 4-oxapentyi, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl.

A ² , A ³ and A ⁴ are preferably Cy or Ph. In the compounds of the formulas above and below, Ph is preferably a 1,4-phenylene- (Phe), a pyrimidine-2,5-diyl- (Pyr), a pyridine-2,5-diyl- (Pyn), a pyrazine-3,6-diyl or a pyridazine-2,5-diyl group, more preferably Phe, Pyr or Pyn. Preferably, the compounds of the invention contain no more than one 1,4-phenylene group wherein one or two CH groups are replaced by N. Cy is preferably a trans-1,4-cyclohexylene group. However, particular preference is given to compounds of the formula I in which one of the groups A ² , A ³ and A ^{4 is} a 1,4-cyclohexylene group substituted by CN in the 1 or 4 position and the nitrile group is in the axial position, ie the group A. ² , A ³ and A ^{4 has} the following configuration.

CN

Particularly preferred are compounds of the formula I and the preceding sub-formulas which contain a -Ph-Ph grouping. -Ph-Ph- is preferably -Phe-Phe-, Phe-Pyr or Phe-Pyn. Particularly preferred are the groups

and - (o \ - (o / -, in particular - (O

and also unsubstituted or mono- or polysubstituted by fluorine 4,4'-biphenylyl.

Z ¹ and Z ² are preferably single bonds, secondarily preferably -O-CO-, -CO-O-, -CC = C- or ^ CH ₂ CH ₂ groups.

More preferably Z ¹ is -CO-O-, - 0-CO -, - C = C-or-CH ₂ CH ₂ -, in particular-CH ₂ CH ₂ -and the-C ^ roup CG.

X in the compounds of the formulas above and below denotes halogen, CN or CH ₃ , preferably halogen or CH ₃ .

Halogen is preferably bromine or chlorine, more preferably chlorine.

The preferred meaning of Q ² is alkylene having 1 to 2 carbon atoms, -0 -, - 0-CO -, - COO-and-CH ₂ 0-. Particularly preferred are -CO-O- and -CH ₂ O-, in particular -CO-O. Further preferred meanings of Q ² , in particular in the case X = CH ₃ , are - (CH ₂ Ip -, - (CH ₂ ) P-CO-O ^ (CH ₂ ) PO-CO-u nd- (CH ₂ ) pO -, where ρ 1 to 3 means.

If Q ^{2 is} -CO-O- and -A ⁴ -Z ¹ -A ² -R ^{2 is} 4'-alkoxybiphenyl-4-yl, X is CH ₃ and / or R ^{2 is} -Q ¹ is a group of at least two branches.

If Q ^{2 is} -CO-O-, A ⁴ ^ -A ^{2 is} 4'-biphenyl-4-yl and X is halogen, R ^{2 is} preferably alkyl having 1-12 C atoms (preferably straight-chain or branched-chain alkyl having 4-12 carbon atoms). 10 C atoms), alkenyloxy having preferably 4 to 10 C atoms, perfluoroalkyl or perfluoroalkoxy each having preferably 2 to 10 C atoms, wherein in each case one or more (but not more than half of the CF ₂ groups present) -CHHalogen- and / or-CH ₂ - may be replaced.

Q ¹ is preferably a single bond or alkylene having 1 to 3 C atoms, in which also a CH ₂ group may be replaced by -O-, -O-CO-or -CO-O-.

Particular preference is given to compounds of the formula I which belong to a group

contain. Surprisingly, these compounds show significantly higher values for spontaneous polarization than similar phenylpyrimidine or biphenyl compounds.

Compounds of the formulas above and below with branched wing groups R ¹ and R ² may be of importance.

Branched groups of this kind usually contain no more than two chain branches. R ¹ is preferably a straight-chain group or a branched group having not more than one chain branch.

Preferred branched radicals R ¹ are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), tert-butyl, 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl , 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbotoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl , S-oxa-methylpentyl.

The radical R 1 Q ¹ is an at least single-branched and optionally optically active organic radical having an asymmetric carbon atom. Preferably, the asymmetric carbon atom is then linked to two differently substituted C atoms, a Η-atom and a substituent selected from the group halogen (in particular F, Cl or Br), alkyl or alkoxy each having 1 to 5 C atoms and CN. The optically active organic radical preferably has the

Formula, _ __

-X'-Q ¹ -C * HR ⁵

wherein X 'is -CO-O-, -O-CO ^ -O-CO-O-, -CO-, -O-, -S-, -CH = CH-, -CH = CH-COO- or a single bond .

Q 'alkylene having 1 to 5 C atoms, in which also a non-X'-linked CH ₂ group by -O -, - CO -, - 0-CO -, - CO-O-

or -CH = CH-substituted, or a single bond, Y 'is CN, halogen, methyl or methoxy, and

R ^{5 is} an alkyl group other than Y having 1 to 15 C atoms, wherein also one or two non-adjacent

CH ₂ groups can be replaced by -O-, -CO-, -O-C0-, -CO-O- and / or -CH =CH-,

means.

X 'is preferably -CO-O-O-CO-, -CH = CH-COO- (trans) or a single bond. Particularly preferred

-C0-0 - / - 0-CO- or a single bond

O 'is preferably -CH ₂ -, - CH ₂ CH ₂ -, - CH ₂ CH ₂ CH ₂ - or a single bond, most preferably one

Single bond.

Y 'is preferably CHs ^ CN or Ci, most preferably CN.

R ⁵ is preferably straight-chain or branched alkyl having 1 to 10, in particular 1 to 7, carbon atoms.

Among the compounds of the formula I, preference is given to those in which X and Y 'are not simultaneously methyl.

Among the compounds of the formula I and Ia to Iq, preference is given to those in which at least one of the radicals contained therein has one of the preferred meanings given.

Particular preference is given to compounds of the formula I in which R ^{2 is} a straight-chain alkyl or perfluoroalkyl group having in each case 1-12, preferably 5-12, carbon atoms, in which one or more CH ₂ -bzw. CF ₂ groups by a grouping selected from the group -O -, - S -, - C0 -, - OCO -, - O-COO-, -C0-0- and -CH = CH- or by a combination of two suitable groups may be replaced, wherein two heteroatoms are not directly linked.

Accordingly, R ² preferably denotes alkyl, -O-alkyl- ₁ -S-alkyl- _7- O-CO-AIkYl or -COO-alkyl, wherein alkyl is a straight-chain alkyl, alkenyl, perfluoroalkyl or polyfluoroalkyl group, each having 1-12 C Atoms, preferably straight-chain alkyl.

A small group of particularly preferred meanings for optically active radicals R ¹ in these preferred compounds is given below:

-OC * HCH3-n-alkyl, -O-CH ₂ -C * HCH ₃ n-alkyl, -O-CH ₂ -CH ₂ -C * HCH3-n-alkyl, -O-CH ₂ -CH ₂ - CH ₂ -C * HCH ₃ -n-alkyl, -C * HCH ₃ -n-alkyl, -CH ₂ -C * HCH ₃ -n-alkyl, -COO-C * CHCH ₂ -n-alkyl-, -COO- CH ₂ -C * HCH ₃ -n-alkyl, -O- ^ HCHr-COO-n-alkyl, -OC * HCH ₃ -CHr-on-alkyl, -OCO-C * HCI-n-alkyl, -OCO- ^ HCI-CHCH ₃ -Ch ₃ , -OCO-C * HCI-C * HCHa-C ₂ H ₅ , -OCO-C 1 -C 4 -CH ₂ -CHCH ₃ -Ch ₃ , -OCO-C * HCl-C ( CH ₃ ) ₃ , -COO-C * HCH ₃ -COO n-alkyl, -O-CO-C * HCH ₃ -On-alkyl, -OCH ₂ -C * HCH ₃ -On-alkyl, -COO- ^ HCH ₃ -CHr-on-alkyl, -OC ^ CHy-CHr-COO-n-alkyl, -COO-C * HCH ₃ -CH ₂ -COO-n-alkyl, -OCH ₂ -C * HCH ₃ -COO- n-alkyl, -COO-CH ₂ -C * HCHj-COO-n-alkyl.

A small group of particularly preferred compounds of formulas 124 to 145 is listed below:

C ₄ Hg-C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -OC _e H ₁₃ 124

C ₃ H ₇ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) n -OC _e H ₁₃ 125

C ₂ H ₅ -C * HCH ₃ -C * CHCI-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³⁾ _n -OC ₇ F _l5 126

C ₂ H ₅ -C * HCH ₃ -C * CHCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -OCH ₂ C ₆ F ₁₃ 127

CH ₃ -CHCH ₃ -C * CHCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -O-CH ₂ -CH = - ₃ H ₇ 128

CH ₃ -CHCH ₃ -C 2 Cl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -O-CH ₂ CH ₂ -OC ₃ H ₇ 129

CH ₃ -CHCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -CH ₂ -OC ₅ H ₁₁ 130

CH ₃ -CHCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₈ H ₁ 7 131

CH ₃ -CHCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₇ H _{15 5} 132

C ₂ H _s -C * HCH ₃ -C * HC! -COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₆ H ₁₃ 133

C ₂ H ₅ -C * HCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₉ H ₁₉ 134

(CH ₃ ) ₃ -C * HCi-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -OC ₆ H ₁₃ 135

(CH ₃ ) ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₆ H ₁₃ 136

CH ₃ -CHCH ₃ -C * HBr-COO-A ⁴ -Z ¹ -A ² -7 (Z ² -A ³ ) _n -OC ₇ H ₁₅ 137

CH ₃ -CHCH ₃ -C * HBr-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₇ H ₁₅ 138.

CH ₃ -CHCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₆ F ₁₃ 139

CH ₃ -CHCH ₃ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₇ F ₁₃ 140

C ₂ H _r -C * HCH ₃ -C * HF-COO-A ⁴ -Z ¹ -A ² - {Z ² -A ³ ) n _{-OC 6} H ₁₃ 141

C ₂ H _ff -C * HCH ₃ -C * HF-COO-A ⁴ -Z ¹ -A ² - <Z ² -A ³ ) _n -C ₆ H ₁₃ . 142

C ₂ H ₅ -C * HCH ₃ -C * HCI-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n - (CF ² ) ₃ CH ₃ 143

C ₄ H ₉ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₉ H ₁₉ 144

C ₃ H ₇ -C * HCl-COO-A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -C ₇ H ₁₄ 145

In the compounds of the formula I and in the preceding and following sub-formulas, -A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _{n is} preferably a group of the following formulas 1 to 16 or their mirror image:

_ ^ ö) - ^ ö) _ _ <2) _ ^> - (P = 1, 2, 3, or 4;

g = O, 1, 2, 3 or 4)

(F) _p (F) _g

-CH ₂ CH ₂ - (O

12

- <O) -CH ₂ CH ₂

C = C

15

16

Groups of the formulas 1,5,7,9,10,11,12,13 and 14, especially those of the formulas 5 and 7, are particularly preferred. Those of the abovementioned formulas which contain one or more groups Dio, Dit, Pip and / or Pyr each include the two possible 2,5- (Dio, Dit, Pyr) or 1,4-position isomers (Pip). Particular preference is given to compounds of the formula I ',

Alkyl-CHX ° -Q ¹ -C * HX-Q ² -A ⁴ -Z ^l -A ² - (Z ² -A ³ ) _n -R ²

wherein alkyl is an alkyl group having 1 to 7 carbon atoms and X ^{0 is} halogen, CN or CH ₃ and Q ¹ , X, Q ² , A ⁴ , Z ¹ , A ² , Z ² , A ³ , η and R ^{2 are} the have given meanings given in formula I, with the provisos that

(1) X is CH ₃ , if

(a) --A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -R ² 4'-alkoxybiphenyl-4-yl and Q ² -CO-O-, or

(b) -A ¹ -A ² -Z ⁴ - (Z ² -A ³⁾ _n -R ² 4'-Alkanoyloxybiphenyl-4-yl and Q ² -CO-0-or-CH ₂ -0-CO-means , and

(2) at least one of A ² , A ³ and A ⁴

represents fallsAlkyl-CHX ⁰ -Q ¹ -C * HX6-methyl-2-heptylundQ ² -CH ₂ CH ₂ -O-or-CH ₂ CH ₂ -OOC-means.

X ⁰ is preferably CH ₃ , alkyl is preferably methyl or ethyl, most preferably methyl. Particular preference is thus given to compounds of the formula I 'in which R ^{1 is} an isopropyl group. In the preferred compounds of the formula Γ, particular preference is given to those in which X is CH ₃ . Here, Q ¹ is preferably alkylene having 3 C atoms, in which a CH ₂ group may also be replaced by -O-, -O-CO- or -CO-O-. Preferably, however, Q ¹ is -CH ₂ -CH ₂ -CH ₂ -.

In the preferred compounds of the formula I ', O ^{2 is} preferably alkylene having 1 to 3 C atoms, in which also a CH ₂ group is represented by -O-, -CO-O-, -O-C0- and / or -CHHalogen ( Halogen is preferably Cl or Br) may be replaced. Preferred meanings of Q ² are therefore in particular -CH ₂ -, - CH ₂ CH ₂ -, - CH ₂ CH ₂ CH ₂ -, - CH ₂ CH ₂ -O -, - CH ₂ CH ₂ -OOC -, - CH ₂ -CH ₂ -COO-, -CH ₂ -COO -, - CH ₂ -COO-CH ₂ -, - CH-halo-COO and -CHH-halo-CHj-O- Particularly preferred are the compounds of formula! ', Wherein Q is ² -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ - and A ^{4 is} a ring selected from the group

represents.

The preferred meanings for A ² , A ³ , A ⁴ , Z ¹ , Z ² , η and R ² are the same as in formula I.

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

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

Thus, the compounds of the formula I can be prepared by reducing a compound which otherwise corresponds to the formula I but contains one or more reducible groups and / or C-C bonds instead of Η-atoms. Suitable reducible groups are preferably -CH = CH groups, furthermore, for example, free or esterified hydroxy groups, aromatically bonded halogen atoms or carbonyl groups. Preferred starting materials for the reduction correspond to the formula I, but instead of a -CH ₂ CH ₂ group, a -CH = CH group and / or instead of a -CH ₂ group of a -CO group and / or at of a Η-atom contain a free or a functional (eg in the form of its p-toluenesulfonate) facing away from the OH group.

The reduction can z. Example, by catalytic hydrogenation at temperatures between about O ⁰ C and about 200 ° C and pressures between about 1 and 200barin an inert solvent, for. An alcohol such as methanol, ethanol or isopropanol, an ether 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 (eg PtO ₂ , PdO), on a support (eg Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form.

Ketones can also by the methods of Clemensen (with zinc, amalgamated zinc or tin and hydrochloric acid, suitably in aqueous-alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 12O ⁰ C) or Wolff-Kishner (with hydrazine , suitably reduced in the presence of alkali such as KOH or NaOH in a high boiling solvent such as diethylene glycol or triethyl glycol at temperatures between about 100 and 200 ^G C) to the corresponding compounds of formula I containing alkyl groups and / or -CH ₂ CH ₂ bridges , Furthermore, reductions with complex hydrides are possible. For example, arylsulfonyloxy groups may be reductively removed with LiAlH ₄ , in particular p-toluenesulfonyloxymethyl groups may be reduced to methyl groups, suitably in an inert solvent such as diethyl ether or THF at temperatures between about 0 and 100 ° C. Double bonds can be hydrogenated (also in the presence of CN groups!) With NaBH ₄ or tributyltin hydride in methanol; For example, from 1-Cyancyclohexenderivaten the corresponding Cyclohexanderiyate arise.

Esters of formula I can also be obtained by esterification of corresponding carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive derivatives).

Particularly suitable as reactive derivatives of said carboxylic acids are the acid halides, especially the chlorides and bromides, and also the anhydrides, eg. As well as mixed anhydrides, azides or esters, especially alkyl esters with 1-4 carbon atoms in the alkyl group.

Suitable reactive derivatives of said alcohols or phenols are, in particular, the corresponding metal alcoholates or phenolates, preferably an alkali metal such as Na or K.

The esterification is advantageously carried out in the presence of an inert solvent. Particularly suitable are in particular 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 hexamethyltriamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as Dimethyl sulfoxide or sulfolane. Water-immiscible solvents can also be advantageously used to azeotropically distill off the water formed in the esterification. Occasionally, an excess of an organic base, for example 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, for example by simply heating the components in the presence of sodium acetate. The reaction temperature is usually between -50 ° C and + 25O ⁰ C, preferably between -20 ° C and +80 ⁰ C. At these temperatures, the esterification reactions are generally complete after 15 minutes to 48 hours.

In particular, the reaction conditions for the esterification depend largely on the nature of the starting materials used. Thus, a free carboxylic acid is reacted 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 reaction method is the reaction of an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in a basic medium, alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogencarbonates such as sodium carbonate, potassium carbonate or potassium hydrogencarbonate, 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. Another preferred embodiment of the esterification is that the alcohol or phenol is first converted into the sodium or potassium alcoholate or phenolate, z. B. by treatment with ethanolic sodium or potassium hydroxide solution, this isolated and suspended together with sodium bicarbonate or potassium carbonate with stirring in acetone or diethyl ether and this suspension with a solution of the acid chloride or anhydride in diethyl ether, acetone or DMF, advantageously at temperatures between about 25 ° C and +20 ⁰ C. Dioxanderivatebzw. Dithiane derivatives of the formula I are advantageously prepared by reacting a corresponding aldehyde (or one of its reactive derivatives) with a corresponding 1,3-diol or a corresponding 1,3-dithiol (or one of its reactive derivatives), preferably in the presence of an inert solvent such as benzene or toluene and / or a catalyst, e.g. As a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between 2O ⁰ C and about 150 ⁰ C, preferably between 80 ⁰ C and 120 ⁰ C. As a reactive derivatives of the starting materials are in the first place acetals.

The mentioned aldehydes and 1,3-diols or 1,3-dithiols and their reactive derivatives are known in some cases, all of which can be prepared without difficulty by standard methods of organic chemistry from compounds known from the literature. For example, the aldehydes are obtainable by oxidation of corresponding alcohols or by reduction of corresponding carboxylic acids or their derivatives, the diols by reduction of corresponding diesters and the dithiols by reacting corresponding dihalides with NaSH.

For the preparation of nitriles of the formula I, corresponding acid amides, for. For example, those in which instead of the radical X is a CONH ₂ group are dehydrated. The amides are z. B. from corresponding esters or acid halides by reaction with ammonia available. Dehydrating agents are, for example, inorganic acid chlorides such as SOCI _2, PCI _3, PCl _5, POCl _3, SO ₂ Cl _2, COCl _2, further P ₂ O _5, P ₂ S _5, AICI ₃ (z. B. as a double compounds having NaCl), aromatic sulfonic acids and sulfonic acid halides. It can be in the presence or absence of an inert solvent at temperatures between about O ⁰ C and 150 ° C work; suitable solvents are, for example, bases such as pyridine or triethylamine, aromatic hydrocarbons such as benzene, toluene or xylene or amides such as DMF.

For the preparation of the above nitriles of the formula I can also corresponding acid halides, preferably the chlorides, with sulfamide, preferably in an inert solvent such as tetramethylene sulfone, at temperatures between about 80 ° C and 15O ⁰ C, preferably at 120 ⁰ C. After the usual Work-up can be directly isolate the nitriles. Ethers of the formula I are obtainable by etherification of corresponding hydroxy compounds, preferably corresponding phenols, wherein the hydroxy compound is first expediently converted into a corresponding metal derivative, eg. B. by treatment with NaH ₁ NaNH ₂ , NaOH, KOH, Na ₂ Co ₃ or K ₂ CO _{3 is converted} into the corresponding alkali metal or alkali metal phenolate. This can then be reacted with the appropriate alkyl halide, sulfonate or dialkyl sulfate, suitably 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 2O ⁰ C and 100 ⁰ C. In the preparation of nitriles of the formula I and corresponding chlorine or bromine compounds of formula I can be reacted with a cyanide, suitably with a metal cyanide such as NaCN, KCN or Cu ₂ (CN) ₂ , z. B. in the presence of pyridine in an inert solvent such as DMF or N-methylpyrrolidone at temperatures between 2O ⁰ C and 200 ⁰ C. The optically active compounds of formula I is obtained by the use of appropriate optically active starting materials and / or by separation of the optical Antipodes by chromatography according to known methods

 Likewise provided by the invention are aliphatic halogen compounds of the formula 1

R-CHCH ₃ - (CH _{2) m} - [- CHCH ₃ - (CH _{2) o} -] p-CHHalogen-Q-OH 1

where R is alkyl having 1 to 5 C atoms,

m 2 to 5,

ο 0bis3,

ρ 0or1, and

Q is CO or CH ₂ , and their reactive derivatives,

the use of these compounds as intermediates for the synthesis of liquid crystal compounds for ferroelectric ^ liquid crystal mixtures with high spontaneous polarization, and a process for the preparation of liquid crystal compounds with high spontaneous polarization, characterized in that a compound of formula 1 having at least two carbo- and / or heterocyclic rings etherified or esterified hydroxy or carboxy or one of their reactive derivatives. Halogen is preferably chlorine or bromine, particularly preferably chlorine.

The compounds of formula 1 are particularly suitable as intermediates for the preparation of liquid crystal compounds with high spontaneous polarization, z. B. in particular for the preparation of corresponding liquid crystal compounds according to the invention of formula I. previously used a-halogen acids or alcohols (for example, 3-methyl-2-chlorobutyric acid) were prepared in several reaction steps from the corresponding amino acids.

The invention had the object of providing aliphatic halogen compounds and their preparation, which are particularly suitable for easy accessibility and suitability for the preparation of liquid crystal compounds with high spontaneous polarization.

The compounds of the formula 1 can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart) under reaction conditions which are known and suitable for the said reactions. One can also make use of known per se, not mentioned here variants. All starting materials are known from the literature or can be prepared by methods known from the literature.

Preferred starting materials are commercially available optically active alcohols such. For example, 2-methylbutanol or citronellol.

(S) - (-) - Citronellol can be hydrogenated, for example, by known methods and oxidized to (S) -3,7-dimethyloctanoic acid, their reaction with suitable halogenating agents (for example chlorine in the presence of radical scavengers) (2 R, 2 S Higher homologs are accessible by homologation of 3,7-dimethyloctanoic acid, and corresponding halogenation of optically active 5-methylheptanoic acid (obtainable by malonic ester synthesis from 2-methylbutanol) yields, for example, 2-chloro-5-methylheptanoic acid ,

The diastereomer mixtures obtained after the halogenation of the optically active carboxylic acids can be decomposed by chromatographic separation according to methods known per se. However, the chromatographic separation can also be carried out only at the Flüssigkristallendprodukt. The resulting optically active halocarboxylic acids can be reduced to the corresponding alcohols by methods known per se.

From the compounds of formula 1 can be prepared by known methods, such as. For example, esterification or etherification with a variety of known mesogenic building blocks, a variety of liquid crystalline compounds can be prepared.

The compounds of formula 1 accordingly comprise compounds of sub-formulas 1a and 1b:

R-CHCH ₃ - (CH ₂ Ir _n -CHCH ₃ - (CH ₂ ) O-CHHioIObn-Q-OH 1 a

R-CH 2 CH 2 CH 2 -CH 2 -Haiogene Q-O-1b

Compounds of subformula Ia are preferred. R is preferably methyl or ethyl, more preferably methyl, m is preferably 2 or 3, most preferably 3. o is preferably 0.1 or 2. Especially preferred is ο = O. Halogen is preferably chloro or bromo, most preferably chloro.

Also subject of this invention are thus liquid crystal compounds with high spontaneous polarization containing at least two carbo- and / or heterocyclic rings and two wing groups, characterized in that at least one wing group, the structural component of the formula 1a

R-CHCH ₃ - {CH ₂ ) _m - [- CHCH ₃ - (CH ₂ ) _o -] _p -CHHalogen-O-

1a

wherein R, m, ο, ρ and Q have the meanings given above, and ferroelectric liquid-crystalline phases having at least two liquid-crystalline components, characterized in that they at least one compound containing a structural component of the formula 1 a for optimizing the spontaneous polarization

R-CHCHHCH ₂ ) _m - [- CHCH _o3 - (CH ₂ ) _o -] p -CHHalogen-

1a

wherein R, m, ο, ρ and Q have the meanings given above, and liquid crystal display elements, in particular ferroelectric electro-optical display elements, which contain a corresponding phase as liquid-crystalline dielectric.

The phases according to the invention contain at least one, preferably at least two compounds of the formula Particularly preferred are chirally tilted smectic liquid-crystalline phases whose achiral base mixture contains, in addition to compounds of the formula I, at least one other component with a negative or small positive dielectric anisotropy. These further component (s) of the chiral base mixture may constitute 1 to 50%, preferably 10 to 25%, of the base mixture. Compounds of the subformulae Va to Vp are suitable as further components with an amount of small positive or negative dielectric anisotropy:

R ⁴ -foj- COX "- CoJ- R ^E

(F) n

(F) n

R ⁴ - / o ~ \ - / "ÖY-COX" - ζθ \ R ⁴ - / Ö ~ \ - fÖ \ -COX "-R ⁴ - ζθ \ -COX" - fÖ \ -

-R-

R * - <H * -C00- <H £ ~ X H f-R

Va

Vb

Vc

Vd Ve Vf

vg Vh vi

vj

R ⁴ -

, (F) n

vk

R ⁴ - \ _O} - (V) -X ¹¹ CO- ζθ \ -R ⁵ Vl

R ⁴ - Co ) - (oj - OCH ₂ - / OV - R ⁵ Vm

(F) n

R ⁴ - (£> - (T) -CH ₂ O- (T) -R

Vn

R ⁴ - (O) - (O) -COX "- (H * -R" Vo

^l - (o) - io ~ \ -cox ¹¹ - (hV-r ^;

R ⁴ - / - Ö) - / θ) -X ¹¹ CO- / ITV-R ⁵ Vp

Λ- _N N- t /

R ⁴ and R ⁵ are each preferably straight-chain alkyl, alkoxy, alkanoyloxy or alkoxycarbonyl having in each case 3 to 12 C atoms.

X "is O or S, preferably O. η is O or 1.

Particularly preferred are the compounds of sub-formulas Va, Vb and Vf, wherein R ⁴ and R ⁵ each represents straight-chain alkyl or alkoxy each having 5 to 10 C atoms.

The compounds of sub-formulas Vc, Vh and Vi are useful as melting point depressant additives and are normally added to the base mixtures at not more than 5%, preferably 1 to 3%. R ⁴ and R ⁵ in the compounds of the sub-formulas Vc, V h and Vi are preferably straight-chain alkyl having 2 to 7, preferably 3 to 5, C atoms. Another class of compound which is suitable for lowering the melting point in the phases according to the invention is that of the formula

J I J \

O> -OOC-R ⁵

wherein R ⁴ and R ^{5 have} the preferred meaning given for Vc, Vh and Vi.

Further suitable components with negative dielectric anisotropy are compounds containing the structural element M, N or O.

CN CN Cl _ / VL -CH ₂ -CH- -CH-

M N

Preferred compounds of this type correspond to the formulas VIb and VIc:

R'-Q ¹ -CH ₀ -CH-Q ² -R ^{! I} VIb.

² I

CN

R'-Q ³ -Q ⁴ -R ^f "VIC

R 'and R "are each preferably straight-chain alkyl or alkoxy groups having in each case 2 to 10 C atoms. Q ¹ and Q ^{2 are} each 1,4-phenylene, trans-1,4-cyclohexylene, 4,4'- E3iphenylyl, 4- (trans-4-cyclohexyl) -phenyl, trans, träns-4,4'-bicyclohexyl or one of the groups Q ¹ and Q ^{2 are} a single bond.

Q ³ and Q ^{4 are} each 1,4-phenylene, 4,4'-biphenylyl or trans-1,4-cyclohexylene. One of the groups Q ³ and Q ⁴ may also denote 1,4-phenylenes in which at least one CH group has been replaced by N. R '"is an optically active radical having a symmetrical carbon atom of the structure

 ~ ci "cn

I i

· -Or -CH * -.

Particularly preferred compounds of the formula VIc are those of the formula VI c'j

<oV alkyl

wherein A is 1,4-phenylene or trans-1,4-cyclohexylene, Z ° is CH or N or η is 0 or 1.

The compounds of the formula I are also suitable as components of nematic liquid-crystalline phases, for. B. to avoid reverse twist.

These liquid-crystalline phases according to the invention consist of 2 to 25, preferably 3 to 15 components, including at least one compound of the formula I. The other constituents are preferably selected from the nematic or nematogenic substances, in particular the known substances, from the classes of azoxybenzenes, benzylideneanilines, Biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalene, 1,4-biscyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridazines and their N-oxides, phenyl or cyclohexyldioxanes, phenyl or cyclohexyl-1,3-dithiane, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, 1-phenyl-2-cyclohexylethane, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted cinnamic acids.

The most important compounds which can be considered as constituents of such liquid-crystalline phases can be characterized by the formula Γ,

R'-L-G-E-R "I '

where L and E are each a carbo- or heterocyclic ring system of the 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 tetrahydronaphthaltine, quinazoline and tetrahydroquinazoline,

-CH = CH- -N (O) = N- -CH = CY- -CH = N (O) - -C = C- -CH ₂ -CH ₂ - -CO-O- -CH ₂ -O- -CO-S- -CH ₂ -S- -CH = N- -COO-Phe-COO-

or a C-C single bond,

Y is halogen, preferably chlorine, or-CN, and

R 'and R "is alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these radicals also CN, NC, NO ₂ , CF ₃ , F, Cl or Br.

In most of these compounds R 'and R "are different from each other, one of these radicals usually being an alkyl or alkoxy group, but other variants of the substituents provided are also common Many of these substances or mixtures thereof are commercially available The phases according to the invention contain about 0.1 to 99, preferably 10 to 95%, of one or more compounds of the formula I. Further preferred are liquid-crystalline phases according to the invention containing 0.1-40, preferably 0.5 -30% of one or more compounds of the formula I.

The preparation of the phases according to the invention is carried out in a conventional manner. In general, the components are dissolved in each other, useful at elevated temperature. By means of suitable additives, the liquid-crystalline phases according to the invention can be modified so that they can be used in all hitherto known types of liquid-crystal display elements.

Such additives are known in the art and described in detail in the literature. For example, conductive salts, preferably ethyldimethyldodecylammonium ^ -hexyloxybenzoate tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, BI Haller et al., Mol. Cryst. Liq. Cryst., Vol. 24, pp. 249-258 [1973]). for improving the conductivity, pleochroic dyes for producing colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases are added.

Such substances are e.g. in DE-OS 2209127, 2240864, 2321 632, 2338281, 2450088, 2637430, 2853728 and 2902177.

embodiments

The following examples are intended to illustrate the invention without limiting it. F. = melting point, K. = clearing point. Above and below, percentages are by weight; All temperatures are in degrees Celsius. "Working up" means adding water, extracting with methylene chloride, separating, drying the organic phase, evaporating and purifying the product by crystallisation and / or chromatography.

K: crystalline solid state, S: smectic phase (the index indicates the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase. The number between two symbols indicates the transformation temperature in degrees Celsius.

Example 1:

A mixture of 8 g of (S, S) -3-methyl-2-chloropentanoic acid, 16 g of p- (5-n-octylpyrimidin-2-yl) phenol, 11.6 g of N, N-dicyclohexylcarbodiimide, 0.6 g of 4-N, N- Dimethylaminopyridine and 300 ml of dichloromethane are stirred overnight at room temperature. After filtering off the precipitated urea derivative, the filtrate is washed with dil. Hydrochloric acid and H ₂ O and the org. Phase worked up as usual. There is obtained (S, S) -3-methyl-2-chloropentanoic acid p- (5-n-octylpyrimidin-2-yl) -phenyl ester.

Analog are produced:

3-Methyl-2-chloropentanoic acid p- (5-pentylpyrimidin-2-yl) phenyl ester 3-Methyl-2-chloropentanoic acid p- (5-hexylpyrimidin-2-yl) -phenyl ester S-methyl-1-chloro-pentanoic acid p-fS-heptylpyrimidine ^ -yO-phenyl ester, F.59 °, K (-20 °) S-methyl ^ -chloro-pentanoic acid p-felonylpyrimidine ^ -yl-J-phenyl ester S-methyl-chloro-pentanoic acid p-iB- 3-methyl-2-bromopentanoic acid p- (5-pentylpyrimidin-2-yl) -phenyl ester 3-methyl-2-bromopentanoic acid p- (5-hexylpyrimidin-2-yl) -phenyl ester 3-methyl-2-bromopentanoic acid 3- Methyl 2-bromopentanoic acid p- (5-heptylpyrimidin-2-yl) -phenyl ester 3-Methyl-2-bromopentanoic acid p- (5-octylpyrimidin-2-yl) -phenyl ester 3-methyl-2-bromopentanoic acid p- (5-nonylpyrimidin-2-yl) -phenyl ester 3-Methyl-2-bromopentanoic acid p- (5-decylpyrimidin-2-yl) -phenyl ester 3-methyl-2-chloropentanoic acid p- (5-pentylpyrazin-2-yl ) -phenyl ester 3-methyl-2-chloropentanoic acid p- (5-hexylpyrazin-2-yl) -phenyl ester 3-methyl-2-chloropentanoic acid p- (5-heptylpyrazin-2-yl) -phenyl ester S-methyl ^ - chlorine penta acid p-fö-octylpyrazin ^ yo-phenyl 3-Methyl-2-chloropentanoic acid p- (5-nonylpyrazin-2-yl) -phenyl ester 3-Methyl-2-chloropentanoic acid p- (5-decylpyrazin-2-yl) -phenyl ester 3-methyl-2-chlorohexanecarboxylic acid -p- (5-pentylpyrimidin-2-yl) -phenyl ester S-methyl ^ -chlorohexanecarboxylic acid p-fö-hexylpyrimidine ^ -yD-phenyl ester S-methyl ^ -chlorohexanecarboxylic acid p-fö-heptylpyrimidine ^ -yliphenyl ester 3- Methyl 2-chlorohexanecarboxylic acid p- (5-octylpyrimidin-2-yl) phenyl ester S-Methyl ^ -chlorohexanecarboxylic acid p-io-nonylpyrimidine ^ -yO-phenyl ester 3-Methyl-2-chlorohexanecarboxylic acid p- (5-decylpyrimidine 2-yl) -phenyl ester 3-chloro-2-methylpentanoic acid p- (5-pentylpyrimidin-2-yl) -phenyl ester 3-chloro-2-methylpentanoic acid p- (5-hexylpyrimidin-2-yl) -phenyl ester 3 -Chloro-2-methylpentanoic acid p- (5-heptylpyrimidin-2-yl) -phenyl ester S-chloro-methylpentanoic acid p-iB-octylpyrimidine ^ -yll-phenylester S-chloro-methylpentanoic acid p-iso-nonylpyrimidine ^ -yO-phenyl ester S-chloro-methyl-pentanoic acid p-i-decylpyrimidine-phenyl-3-bromo-2-methyl-pentanoic acid p- (5-pen tylpyrazine-2-yl) -phenyl ester 3-Bromo-2-methyl-pentanoic acid p- (5-hexylpyrazino-2-yl) -phenyl ester 3-Bromo-2-methyl-pentanoic acid p- (5-heptyl-pyrazino-2-yl) -phenyl ester 3-Bromo-2-methylpentanoic acid p- (5-octylpyrazin-2-yl) -phenyl ester 3-Bromo-2-methylpentanoic acid p- (5-nonylpyrazine-2-yl) -phenyl ester 3-bromo-2-methylpentanoic acid p- (5-decylpyrazine-2-yl) -phenyl ester 3-methyl-2-chlorobutyric acid p- (5-butylpyrimidin-2-yl) -phenyl ester 3-methyl-2-chlorobutyric acid p- (5-pentylpyrimidine-2 -yl) -phenyl ester 3-methyl-2-chlorobutyric acid p- (5-hexylpyrimidin-2-yl) -phenyl ester 3-methyl-2-chlorobutyric acid p- (5-heptylpyrimidin-2-yl) -phenyl ester, m. 64 °, K (-10 °)

S-Methyl ^ -chlorobutyric acid p-fB-octylpyrimidine ^ -yO-phenyl ester 3-Methyl-2-chlorobutyric acid p- (5-nonylpyrimidin-2-yl) -phenyl ester S-methyl-W-chlorobutyric acid p-fB-decylpyrimidine ^ -yD-phenyl ester 3-methyl-2-chlorobutyric acid p- (5-undecylpyrimidin-2-yl) -phenyl ester 3-methyl-2-chlorobutyric acid p- (5-dodecylpyrimidin-2-yl) -phenyl ester 4-methyl- 2-chloropentanoic acid p- (5-butylpyrimidin-2-yl) -phenyl ester 4-Methyl-2-chloropentanoic acid p- (5-pentylpyrimidin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (5 -hexylpyrimidin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (5-heptylpyrimidin-2-yl) -phenyl ester, m.

4-Methyl-2-chloropentanoic acid p- (5-octylpyrimidin-2-yl) -phenyl ester 4-Methyl-2-chloropentanoic acid p- (5-nonylpyrimdin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (5-Decylpyrimidin-2-yl) -phenyl ester 4-Methyl-2-chloropentanoic acid p- (5-undecylpyrimidin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (5-dodecylpyrimidine-2 -yl) -phenyl ester 3,3-dimethyl-2-chlorobutyric acid p- (5-butylpyrimidin-2-yl) -phenyl ester SjS-dimethyl ^ -chlorobutyric acid p-iB-pentylpyrimidine ^ -yD-phenyl ester 3,3-dimethyl -2-chlorobutyric acid p- (5-hexylpyrimidin-2-yl) -phenyl ester S ^ -dimethyl ^ -chlorobutyric acid p-fö-heptylpyrirnidine ^ -yl-phenylester 3,3-dimethyl-2-chlorobutyric acid p- (5 -octylpyrimidin-2-yl) -phenyl ester S ^ -dimethyl- ^ -chlorobutyric acid p-iB-nonylpyrimidine ^ -yD-phenyl ester 3,3-dimethyl-2-chlorobutyric acid p- (5-decylpyrimidin-2-yl) - phenyl ester 3,3-dimethyl-2-chlorobutyric acid p- (5-undecylpyrimidin-2-yl) -phenyl ester

S, -dimethyl-chlorobutyric acid p-IB-dodecylpyrimidine - ^ - yO-phenyl ester "

S-Methyl ^ -chlorobutyric acid p-fp-n-decylphenyD-phenyl ester 3-Methyl-2-chlorobutyric acid p- (pn-nonylphenyl) -phenyl ester 3-Methyl-2-chlorobutyric acid p- (pn-octylphenyl) -phenyl ester S-methyl ^ -chlorobutyric acid p-fp-n-heptylphenyD-phenyl ester 3-methyl-2-chlorobutyric acid p- (pn-heptenylphenyl) -phenyl ester S-methyl ^ -chlorobutyric acid p-fp-n-hexylphenyO-phenyl ester S -Methyl ^ -chlorobutyric acid p-lp-n-pentylphenyD-phenylester S-methyl ^ -chlorobutyric acid p-fp-n-butylphenyD-phenylester S-methyl ^ -chlorobutyric acid p-lp-n-perfluorobutylphenyO-phenylester

S-methyl ^ chlorobutyric acid-p-lp-n-perfluorhexylphenyO-phenyl ester

3-Methyl-2-chlorobutyric acid p- (pn-perfluorooctylphenyl) -phenyl ester S-methyl ^ -chlorobutyric acid p-lp-n-perfluorohexylethylphenyO-phenyl ester S-methyl ^ -chlorobutyric acid p-lp-n-perfluorooctanoyloxyphenyld-phenylester S -Methyl ^ -chlorobutyric acid-p-fp-n ^^. S ^^^ - hexafluorobutoxyphenyl O-phenyl ester S-methyl ^ -chlorobutyric acid p-lp-n-IJ ^ -trihydroperfluoroheptoxyphenyl -phenyl ester 3-methyl-2-chlorobutyric acid-p - (pn-1,1,5-trihydroperfluoropentoxyphenyl) phenyl ester S-methyl ^ -chloropentanoic acid p-fp-decylphenyD-phenyl ester 3-methyl-2-chloropentanoic acid p- (p-nonylphenyl) -phenyl ester S-methyl ^ - chloropentanoic acid p-lp-octylphenyO-phenyl ester S-methyl ^ -chloro-pentanoic acid p-lp-heptylphenyD-phenyl ester S-methyl ^ -chloro-pentanoic acid p-lp-heptenylphenyl-1-phenylester S-methyl ^ -chloro-pentanoic acid-p-lp-hexylphenylj- phenyl ester, mp 68 ° C 3-Methyl-2-chloropentanoic acid p- (p -pentylphenyl) -phenyl ester 3-methyl-2-chloropentanoic acid p- (p-butylphenyl) -phenyl ester 3-methyl-2-chloropentanoic acid p - (p-perfluorbutylphenyl) -phenyleste r S-methyl-1-chloropentanoic acid p-lp-perfluorohexylphenyO-phenyl ester S-methyl-1-chloro-pentanoic acid p-lp-perfluorooctyl-phenyl-3-methyl-2-chloro-pentanoic acid p- (p-perfluorohexylethylphenyl) -phenyl ester S-methyl ^ -chloro-pentanoic acid p-fp-perfluorooctanoyloxyphenyl -phenyl ester 3-methyl-2-chloro-pentanoic acid p- (p-2,2,3,4,4,4-hexafluorobutoxyphenyl) -phenyl ester S-methyl-1-chloro-pentanoic acid p-lp- IJJ-trihydroperfluoroheptoxyphenyl O-phenyl ester S-methyl-1-chloropentanoic acid p-lp-i ^^ - trihydroperfluoropentoxyphenyl J-phenyl ester

Example 2:

With exclusion of moisture at ⁰ ° C., a mixture of 4.9 g of hydroquinone-4-cyano-4-octylcyclohexanecarboxylic acid ester (obtainable by esterification of 4-cyano-4-octylcyclohexanecarboxylic acid with hydroquinone monobenzyl ether and subsequent removal of the benzyl group by catalytic hydrogenation), 1, 87g of optically active 2-chloro-3-methylbutyric acid and 170 mg of 4-N, N'-dimethylaminopyridine in 30 ml of dichloromethane are added dropwise 3.1 g of dicyclohexylcarbodiimide in 5 ml of dichloromethane. After stirring for 12 hours at room temperature, filtration and customary work-up of the filtrate gives optically active 2-chloro-3-methylbutyric acid p- (4-cyano-4-octylcyclohexylcarbonyloxy) phenyl ester.

Analog are produced:

2-Chloro-3-methylbutyric acid p- (4-cyano-4-decylcyclohexylcarbonyloxy) -phenyl ester 2-Chloro-3-methylbutyric acid p- (4-cyano-4-nonylcyclohexylcarbonyloxy) -phenyl ester 2-chloro-3-methylbutyric acid p- (4-Cyano-4-heptylcyclohexylcarbonyloxy) -phenyl ester 2-Chloro-3-methylbutyric acid p- {4-cyano-4-hexylcyclohexylcarbonyloxy) -phenyl ester

2-Chloro-3-methylbutyric acid p- (4-cyano-4-decylcyclohexyloxycarbonyl) -phenyl ester 2-Chloro-3-methylbutyric acid p- (4-cyano-4-nonylcyclohexyloxycarbonyl) -phenyl ester 2-chloro-3-methylbutyric acid p- (4-Cyano-4-heptylcyclohexyloxycarbonyl) -phenyl ester 2-Chloro-3-methylbutyric acid p- (4-cyano-4-hexylcyclohexyloxycarabonyl) -phenyl ester

Example 3:

0.1 mol of 4- (p-pentyloxyphenyl) benzylnitrile and 0.3 mol of (S) -1-bromo-2-methylbutane are dissolved in 70 ml of toluene, mixed with 0.11 mol of NaNH ₂ (50% in toluene) and boiled 5 hours. The usual work-up gives 4'-pentyloxy-4- (1-cyano- (S) -3-methylpentyl) biphenyl.

Analog are produced:

4'-hexyloxy-4- (1-cyano-3-methylpentyi) biphenyl

4'-heptyloxy-4- (1-cyano-3-methylpentyl) biphenyl

4'-octyloxy-4- (1-cyano-3-methylpentyl) biphenyl

4'-nonyloxy-4- (1-cyano-3-methylpentyl) biphenyl

4'-decyloxy-4- (1-cyano-3-methylpentyl) biphenyl

4'-Pentyl-4- (1-cyano-3-methylpentyl) biphenyl

4'-hexyl-4- (1-cyano-3-methylpentyl) biphenyl

4'-heptyl-4- (1-cyano-3-methylpentyl) biphenyl

4'-octyl-4- (1-cyano-3-methylpentyl) biphenyl

4'-nonyl-4- (1-cyano-3-methylpentyl) biphenyl

4'-decyl-4- (1-cyano-3-methylpentyl) biphenyl

4 '- (4-pentylcyclohexyl) -4- (1-cyano-3-methylpentyl) biphenyl 4' - (4-hexylcyclohexyl) -4- (1-cyano-3-methylpentyl) biphenyl 4 '- (4-heptylcyclohexyl) -4- (1-cyano-3-methylpentyl) biphenyl 4 '- (4-octylcyclohexyl) -4- (1-cyano-3-methylpentyl) biphenyl 4' - (4-nonylcyclohexyl) -4- (1-cyano) 3-methylpentyl) biphenyl 4 '- (4-Decylcyclohexyl) -4- (1-cyano-3-methylpentyi) biphenyl 4- (4-Pentylcyclohexyl) - (1-cyano-3-methylpentyl) benzene 4- (4-Hexylcyclohexyl ) - (1-cyano-3-methylpentyl) benzene 4- (4-Heptylcyclohexyl) - (1-cyano-3-methylpentyl) benzene 4- (4-octylcyclohexyl) - (1-cyano-3-methylpentyl) benzene 4- (4-Nonylcyclohexyl) - (1-cyano-3-methylpentyl) benzene 4- (4-Decylcylohexyl) - (1-cyano-3-methylpentyl) -benzene S-Pentyl-tp-d-cyano-S-methylpenty-diphenyl-1-pyrimidine S-Hexyl-tp-O-cyano-S-methylpentyl-phenyl-pyrimidine 5-Heptyl-2- [p- (1-cyano-3-methyl-pentyl) -phenyl] -pyrimidine S-octyl-1-P-O-cyano-S -methylpentyOphenyll-pyrimidine 5-Nonyl-2-fp- (1-cyano-3-methylpentyl) -phenyl] -pyrimidine B-decyl-tp-cyano-S-methylpentyl-1-phenyl-pyrimidine.

Example 4:

A mixture of 5.3 g of p- [p- (4-cyano-4-octyl-cyclohexyl) -phenyl] -phenol (obtainable by alkaline ether cleavage from r-1-cyancis-4- (4'-propyloxybiphenyl-4-yl ) -1-octyl cyclohexane with potassium tert-butoxide in NMP at 180 ⁰ C), 1.9 g of optically active 2-chloro-3-methyl-butyric acid, and 170g of DMAP are suspended in 40 ml CH ₂ CI. ₂ Then 3.1 g of DCC in 5 ml of CH ₂ Cl _{2 are} added dropwise at ⁰ ° C. and the mixture is stirred at room temperature for 12 hours. After removal of the Dicyclohexylhamstoffes and usual workup gives optically active 2-chloro-3-methyl-butyric acid 4 '- (4-cyano-4-octylcyclohexyl) -biphenyl-4-yl ester, K.81 S _A 1381st

Analog are produced:

2-Chloro-3-methylbutyric acid 4 '- (4-cyano-4-nonylcyclohexyl) biphenyl-4-yl ester 2-Chloro-3-methylbutyric acid 4' - (4-cyano-4-decylcyclohexyl) -biphenyl 4-yl ester 2-chloro-3-methylbutyric acid 4 '- (4-cyano-4-heptylcyclohexyl) -biphenyl-4-yl ester 2-chloro-3-methylbutyric acid 4' - (4-cyano-4-yl) 4-hexylcyclohexyl) -biphenyl-4-yl-ester 2-Chloro-3-methylbutyric acid 4 '- (4-cyano-4-pentylcyclohexyl) -biphenyl-4-yl-ester 2-Chloro-3-methy pentanoic acid-4 '- (4-Cyano-4-nonylcyclohexyl) -biphenyl-4-yl-ester 2-Chloro-3-methylpentanoic acid 4' - (4-cyano-4-decylcyclohexyl) -biphenyl-4-yl-ester 2-Chloro 2-methylpentanoic acid 4 '- (4-cyano-4-heptylcyclohexyl) biphenyl-4-yl ester 2-chloro-3-methylpentanoic acid 4' - (4-cyano-4-hexylcyclohexyl) -biphenyl-4- yl-ester 2-Chloro-3-methylpentanoic acid 4 '- (4-cyano-4-penty) cyclohexyl) -biphenyl-4-yl-ester 2-Chloro-4-methylpentanoic acid 4' - (4-cyano-4 non-nylcyclohexyl) -biphenyl-4-yl-ester 2-chloro-4-methylpentanoic acid 4 '- (4-cyano-4-decylcyclohexyl) -biphenyl-4-yl-ester 2-chloro-4-methylpentanoic acid 4'- (4-cyano-4-heptyl lyclohexyl) -biphenyl-4-yl-ester 2-chloro-4-methylpentanoic acid 4 '- (4-cyano-4-hexylcyclohexyl) -biphenyl-4-yl-ester 2-chloro-4-methylpentanoic acid 4' - ( 4-cyano-4-pentylcyclohexyl) -biphenyl-4-yl-ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-decylbiphenyl-4-yl) cyclohexyl] - ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-nonyl-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 2- [r 1-cyano-cis-4- (4'-octyl-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-heptylbiphenyl- 4-yl) -cyclohexyl] -ethylestBr 2-Chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-hexylbiphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3 -methylbutyric acid 2- [r-1-cyano-cis-4- (4'-pentyl-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis] 4- (4'-Butyl-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-Chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-decoxy-biphenyl-4-yl) -cyclohexyl ] ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-non oxybiphenyl-4-yl) -cyclohexyi] -ethyl ester

2-Chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-octoxy-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1 Cyan-cis-4- (4'-heptoxybiphenyl-4-yl) cyclohexyl] ethyl ester 2-Chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- {4'-hexoxybiphenyl-4 -yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 2- [r-1-cyano-cis-4- (4'-pentoxybiphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3- Methyl butyric acid 2- [r-1-cyano-cis-4- (4'-butoxy-biphenyl-4-yl) -cyclohexyl] -ethyl ester 2-Chloro-3-methylbutanoic acid 2- [r-1-cyano-cis-4 (4'-propoxybiphenyl-4-yl) -cyclohexyl] -ethyl ester 2-chloro-3-methylbutyric acid 1- {p- [p- (4-cyano-4-hexylcyclohexyl) -phenyl] -phenoxy} - 2-propyl ester 2-Chloro-3-methylbutyric acid 1- {p- [p- (4-cyano-4-butylcyclohexyl) -phenyl] -phenoxy} -2-propyl ester 2-Chloro-3-methylbutyric acid 1- {p - [p- (4-Cyano-4-pentylcyclohexyl) -phenyl] -phenoxy} -2-propyl-2-chloro-3-methylbutanoic acid 1- {p- [p- (4-cyano-4-heptylcyclohexyl) -phenyl ] -phenoxy} -2-propyl ester 2-chloro-3-methylbutyric acid 1- {p- [p- (4-cyano) 4-octylcyclohexyl) -phenyl] -phenoxy} -2-propyl ester 2-Chloro-3-methylbutyric acid 1- {p- [p- (4-cyano-4-hexylcyclohexyl) -phenyl] -phenoxy} -2-ethyl ester 2 -Chloro-3-methylbutanoic acid 1- {p- [p- (4-cyano-4-butylcyclohexyl) -phenyl] -phenoxy} -2-ethyl ester 2-chloro-3-methylbutyric acid 1- {p- [p- (4-cyano-4-pentylcyclohexyl) -phenyl] -phenoxy} -2-ethyl ester 2-chloro-3-methylbutanoic acid 1- {p- [p- (4-cyano-4-heptylcyclohexyl) -phenyl] -phenoxy} 2-ethyl ester 2-chloro-3-methylbutanoic acid 1- {p- [p- (4-cyano-4-octylcyclohexyl) phenyl] phenoxy} -2-ethyl ester

Example 5:

By esterification of 4- (4'-Heptyloxybiphenyl-4-yl) -1-cyano-1- (2-hydroxypropyl) -cyclohexane (available from 4- (4'-Heptyloxybiphenyl-4-yl) -cyclohexanbarbonitrile by alkylation with optical active propylene oxide and lithium diisopropylamide as the base) with optically active 2-chloro-3-methylbutyric acid to obtain optically active 1- [4-cis (4'-Heptyloxybiphenyl-4-yl) -r-1-cyancyclohexyl] -2-propyl- (2-chloro-3-methyl butyrate).

Analog are produced:

1- [4-cis- (4'-Heptyloxybiphenyl-4-yl) -r-1-cyano-cyclohexyl) -2-ethyl- (2-chloro-3-methyl-butyrate) 1- [4-cis (4'-octyloxy-biphenyl 4-yl) -r-1-cyano-cyclohexyl) -2-ethyl- (2-chloro-3-methyl-butyrate) 1- [4-cis (4'-N-phenyl-4-yl) -r-1-cyano-cyclohexyl] 2-ethyl- (2-chloro-3-methyl-butyrate) 1- [4-cis- (4'-decyloxy-biphenyl-4-yl) -r-1-cyano-cyclohexyl] -2-ethyl- (2-chloro-3-) methyl butyrate) 1- [4-cis (4'-hexyloxybiphenyl-4-yl) -1-cyano-cyclohexyl] -2-ethyl- (2-chloro-3-methyl-butyrate)

Example 6:

0.01 mol of levorotatory 3- [4- (5-heptylpyrimidin-2-yl) phenyl (1)] -2-methylpropionic acid (ag ⁰ = -2.3 °), obtained by resolution with (+) -Ephedrine and synthesis of the racemic acid by hydrogenating the corresponding a- methylcinnamic acid over 5% Pd / carbon in tetrahydrofuran, is esterified with 0.01 mol of 2-methylbutanol by literature methods. Obtained after workup and purification 3- [4- (5-Heptylpyrimidin- (2) -yl) phenyl (1)] - 2-methylpropionic acid 2-methylbutylester.

Analog are produced:

3- [4- (5-Propylpyrimidine-2-yl) -phenyl- (1)] -2-methyl-2-propyl-propionate 3- [4- (5-butylpyrimidin-2-yl) -phenyl- (1)] - 2-Methylpropionic acid 2-methylbutyl ester 3- [4- (5-Pentylpyrimidin-2-yl) -phenyl- (1)] -2-methyl-2-propyl-2-propylbutylester 3- [4- (5 -Hexylpyrimidin-2-yl-phenyl- (1)] -2-methylpropionic acid 2-methylbutyl ester 3- [4- (5-octylpyrimidin-2-yl) -phenyl- (1)] -2- 2-methylbutyl methylpropionate 3- [4- (5-nonylpyrimidin-2-yl) -phenyl- (1)] - 2-methyl-2-propyl-2-methylbutyl ester 3- [4- (5-propyloxypyrimidine-2) yl) -phenyl- (1)] - 2-methylpropionic acid 2-methylbutyl ester 3- [4- (5-Butyloxypyrimidin-2-yl) -phenyl- (1)] -2-methylpropionic acid-2 Methyl Butyl Ester 3- [4- (5-Pentyloxypinidine (2) -yl) -phenyl- (1)] -2-methylpropionic acid 2-methylbutyl ester 3- [4- (5-Hexyloxypyrimidin-2-yl) ) -phenyl- (1)] - 2-methylpropionic acid 2-methylbutyl ester 3- [4- (5-Heptyloxypyrimidin-2-yl) -phenyl- (1)] - 2-methyl-2-propionic acid methylbutyl ester 3- [4- (5-Octyloxypyrimidin-2-yl) phenyl (1)) - 2-meth 2-Methylbutyl yl-propionate 3- [4- (5-Nonyloxypyrimidin-2-yl) -phenyl- (1)] - 2-methylpropionic acid 2-methylbutyl ester 3- [4- (5-propylpyrimidine) (2) -yl) -phenyl- (1)] - 2-methylpropionic acid 2-octyl ester 3- [4- (5-Butyl-pyrimidin-2-yl) -phenyl- (1)] - 2-methyl Propionic acid 2-octyl ester 3- [4- (5-Pentylpyrimidin-2-yl) -phenyl] -2-octyl-2-methylpropionate 3- [4- (5-hexylpyrimidine) (2) -yl) -phenyl- (1)] - 2-methylpropionic acid 2-octyl ester 3- [4- (5-heptylpyrimidin-2) -yl) -phenyl (1)] - 2-methyl Propionic acid 2-octyl ester 3- [4- (5-Octylpyrimidin-2-yl) phenyl (1)] -2-methylpropionic acid 2-octyl ester 3- [4- (5-nonylpyrimidine) 2) -yl) -phenyl- (1)] - 2-methylpropionic acid 2-octyl ester 3- [4- (5-propyloxypyrimidin-2-yl) -phenyl- (1)] - 2-methyl- Propionic acid 2-octyl ester 3- [4- (5-Butyloxypyrimidin-2-yl) -phenyl (1)] -2-methylpropionic acid 2-octyl ester 3- [4- (5-pentyloxypyrimidine-2-octyl ester] ) -yl) phenyl (1) l-2-methyl-propionic acid-2-octyl ester

Example 7:

A mixture of 8 g of (S, S) -3-methyl-2-chloropentanoic acid, 16 g of p- (5-n-octylpyridin-2-yl) phenol, 11.6 g of N, N-dicyclohexylcarbodiimide, 0.6 g of 4-N, N-dimethylaminopyridine and 300 ml of dichloromethane are stirred overnight at room temperature. After filtering off the precipitated urea derivative, the filtrate is washed with dil. Hydrochloric acid and H ₂ O and the org. Phase worked up as usual. There is obtained (S ^ lS-methyl ^ -chlorpentahsäure-p-n-octyl pyridine fB-^ -ylJ-phenyl ester, F. 61 ⁰ C.

Analog are produced:

S-Methyl ^ -chloro-pentanoic acid p -fB-pentylpyridine ^ -ylJ-phenyl ester S-methyl ^ -chloro-pentanoic acid p-fS-hexylpyridine ^ -ylJ-phenyl ester 3-methyl-2-chloro-pentanoic acid p- (5-heptyl-pyridine-2 -yl) -phenyl ester S-methyl-W-chloropentanoic acid p-f S -nonylpyridine ^ -yö-phenyl ester S-methyl ^ -chloro-pentanoic acid p-f S -decylpyridine ^ -d-phenyl-ester S-methyl-1-chloro-pentanoic acid p-isl-butylpyridine ^ -yD-phenylester S-Methyl-^ -chloropentanoic acid p-fB-pentylpyridine ^ -ylJ-phenyl ester 3-Methyl-2-chloropentanoic acid p- (5-hexylpyridin-2-yl) -phenyl ester S-methyl ^ -chloro-pentanoic acid -p-fB-heptylpyridine ^ -d-phenylester S-methyl ^ -chloropentanoic acid p-fS-octylpyridine ^ -d-phenylester, mp 66 ° C 3-methyl-2-chloropentanoic acid p- (5-nonylpyridine-2 -yl) -phenyl ester S-methyl ^ -chloropentanoic acid p-fB-decylpyridine ^ -ylj-phenylester S-methyl ^ -chloropentanoic acid p-fB-undecylpyridine ^ -yO-phenylester 4-methyl-2-chloropentanoic acid p- ( 5-dodecylpyridin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (B-butylpyridin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- ( S-pentylpyridin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (S-hexylpyridin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (B-heptylpyridin-2-yl) -phenyl ester 4-Mylthyl-2-chloropentanoic acid p- (B-octylpyridin-2-yl) -phenyl ester 4-methyl-2-chloropentanoic acid p- (S-nonylpyridin-2-yl) -phenylester 4-methyl-2- Chloro-pentanoic acid p- (5-decylpyridin-2-yl) -phenyl ester 4-Methyl-2-chloro-pentanoic acid p- (5-undecylpyridin-2-yl) -phenyl ester 4-Methyl-2-chloro-pentanoic acid p- (S-) dodecyl pyridine-2-yl) -phenyl ester

Example 8:

21.3 g (0.07 mol) of 4-trans-4-octyloxyphenyl) cyclohexanol, 20.2 g of (S) -4- (4,8-dimethyinonyl) benzoic acid (0.07 mol) and 1 g (0.001 mol) DMAP are dissolved in 1X toluene. A solution of 16.0 g of DCC in 40 ml of toluene is added dropwise, the mixture is stirred overnight, chromatographed with toluene over silica gel, crystallized from acetone to give (S) -4- (4,8-dimethylnonyl) benzoic acid [4 - (4-octyloxyphenyl)] - cyclohexyl ester, K76 S ₈ 77 S _A 86Ch 901.

Example 9:

9.1 g (0.03 mol) of 4- (trans-4-octyloxyphenyl) cyclohexanol (m.p. 94.3-9B, 3 ° C, obtainable by reacting 4-octyloxy-phenylmagnesium bromide with 1,4-cyclohexanedione monoethylene ketal, dehydration, catalytic Hydrogenation, ketal cleavage and subsequent reduction with diisobutylaluminum hydride [DIBAH] in toluene), 6.1 g (0.03 mol) of (S) -3,7-dimethyloctanoic acid and 0.14 g (0.13 mmol) of 4-N, N'-dimethylaminopyridine (DMAP) are dissolved in 1 mmol of toluene. A solution of 6.8 g (0.033 mol) of dicyclohexylcarbodiimide (DCC) in 10 ml of toluene is added dropwise at room temperature and stirred overnight, chromatographies on silica gel with toluene, recrystallized from acetone to give (S) -3i7-dimethyloctanoic acid [4 - (4-octyloxyphenyl)] - cyclohexyl ester, m.p. 54.2-5B ° C.

Analog are produced:

(S) -3,7-Dimethyloctanoic acid 4'-pentyloxybiphenyl-4-yl ester (S) -3,7-dimethyloctanoic acid 4'-hexyloxybiphenyl-4-yl ester (S) -3,7-dimethyloctanoic acid 4'-heptyloxybiphenyl -4-yl ester (SJ-SJ-dimethyloctanoic acid, ^ '- octyloxybiphenyl) -yl ester (S) -3,7-dimethyloctanoic acid 4'-nonyloxybiphenyl-4-yl ester (SJ-S, -dimethyloctanoic acid, 1'-decyloxybiphenyl) -yl ester ( S) -3,7-Dimethyloctanoic acid p- (B-pentylpyrimidin-2-yl) phenyl ester (Sl-SJ-dimethyloctanoic acid p-fS-hexylpyrimidine) -yO-phenyl ester (Sl-SJ-dimethyloctanoic acid p-fB- heptylpyrimidine ^ -ylJ-phenyl ester (SJ-SJ-dimethyloctanoic acid p-IB-octylpyridine) -ylJ-phenyl ester (Si-S-dimethyloctanoic acid p-fB-nonylpyrimidine) -yO-phenyl ester, m.p. 44 ° C (monotrophic Sc ) (SJ-SJ-dimethyloctanoic acid p-fB-decylpyrimidine) -butyl-J-phenyl ester (St-SJ-dimethyloctanoic acid p-fB-pentylpyrimidine) -yl-J-phenyl ester (Sl-SJ-dimethyloctanoic acid p-fS-hexylpyrimidine) -butyl -phenyl ester (Si-S-dimethyloctanoic acid p-iB-heptylpyrimidine) -yl-J-phenyl ester (SJ-S-dimethyloctanoic acid p-fB-octylpyrimidine) -xy-phe nyl ester (SJ-SJ-dimethyloctanoic acid p-iB-nonylpyrimidine) -YiJ-phenyl ester (SJ-SJ-dimethyloctanoic acid p-fB-decylpyrimidine) -alkyl-phenyl ester (Sl-SJ-dimethyloctanoic acid p-fp-pentyloxyphenyobenzyl ester (SJ-S)) S ^ -Dimethyloctänsäure-p-fp-hexyloxyphenyöbenzylester (SI-SJ-dimethyl octanoic acid-p-ip-heptyloxyphenyDbenzylester (SJ-SJ-dimethyl octanoic acid-p-fp-octyloxyphenyDbenzylester, F. 40-41 ⁰ C (S) -3,7- Dimethyloctanoic acid p- (p-nonyloxyphenyl) benzyl ester (SJ-SJ-dimethyloctanoic acid p-fp-decyloxyphenyllbenzyl ester (Si-SJ-dimethyloctanoic acid p-fB-pentylpyrimidine) -benzyl ester (Sl-S-dimethyloctanoic acid p-fB-hexylpyrimidine ^ -ylbenzyl ester (Sl-S-dimethyloctanoic acid p-iB-heptylpyrimidine ^ -yl-benzyl ester (Sl-SJ-dimethyloctanoic acid p-IS-octylpyrimidine ^ -ybenzyl ester (S) -3,7-dimethyloctanoic acid p- (B-nonylpyrimidine benzyl -2-yl)

(S) -3,7-Dimethyloctanoic acid p- (5-decylpyrimidin-2-yl) benzyl ester (SI-S-dimethyloctanoic acid p-f S -pentylpyrimidine) -benzylbenzyl ester (S) -3,7-dimethyloctanoic acid p- (5-hexylpyrimidin-2-yl) benzyl ester (S) -3,7-dimethyloctanoic acid p- (5-heptylpyrimidin-2-yl) benzyl ester (SJ-SJ-dimethyloctanoic acid p-IB-octylpyrimidine) -benzyl ester (S1- S, -dimethyloctanoic acid p-iso-nonylpyrimidine ^ -ybenzyl ester (Sl-SJ-dimethyloctanoic acid p-fS-decylpyrimidine) -benzyl ester

Example 10:

20.4 g (50 mmol) of 4- (4'-qctyloxybiphenyl) -cyclohexanecarboxylic acid (obtainable by reacting 4'-octyloxybiphenylmagnesium bromide with 1-cyclohexanedione monoethylene ketal, dehydration, catalytic hydrogenation with H ₂ / Pd-C, ketal cleavage, formation of tosylhydrazone, addition of HCN to the double bond, followed by heating in decalin at 180 ⁰ C and saponification of the nitrile with KOH in diethylene glycol), 7.9 g (S) -3,7-dimethyl octanol and 0.12 g (1 mmol) of DMAP are introduced into 40 ml of toluene , A solution of 9.9 g (55 mmol) of DCC in 15 ml of toluene is added dropwise with stirring at room temperature, stirred overnight and chromatographed on silica gel with toluene. It is recrystallized from toluene to give trans-4- (4'-octyloxybiphenyl-2-yl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester, K104S _B 105 S _A 1151.

Analog are produced:

Trans-4- (4'-Decyloxybiphenyl-4-yl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) -ester trans-4- (4'-nonyloxybiphenyl-4-yl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) trans-4- (4'-heptyloxybiphenyl-4-yl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (4'-hexyloxybiphenyl-4-yl) -cyclohexanecarboxylic acid (3.7- dimethyloctyl) ester trans-4- (4'-pentyloxybiphenyl-4-yl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (p-decyloxyphenyl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) - trans-4- (p-nonyloxyphenyl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (p-octyloxyphenyl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (p-) Heptyloxyphenyl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (p-hexyloxyphenyl) -cyclohexanecarboxylic acid (3,7-dimethyloctyl) ester trans-4- (p-pentyloxyphenyl) -cyclohexanecarboxylic acid (3, 7-dimethyloctyl) ester p-f S -decylpyrimidine ^ -ylj-benzoic acid O -dimethyloctyDoester p- (5-nonylpyrimidin-2-yl) benzoic acid (3,7-dimethyloctyl) - p-oo-octylpyrimidine-α-butylbenzoic acid OJ-dimethyloctyl ester p-fö-heptylpyrimidine-α-yl-benzoic acid OJ-dimethyloctyo-O, F. 40,8-42,3 ⁰ C p- (5- hexylpyrimidine-2-yl) -benzoic acid- (3,7-dimethyloctyl) ester

p- (5-Pentylpyrimidin-2-yl) benzoic acid (3,7-dimethyloctyl) ester -

p-io-Decylpyrimidine ^ -yl-benzoic acid OJ-dimethyloctyo-o-p-fe-nonylpyrimidine ^ -yl-benzoic acid OJ-dimethyloctyl-ester p- (5-octyloxy-biphenyl-4-yl) -cyclohexanecarboxylic acid (3,7 -dimethyloctyl) ester p- (5-heptylpyrimidin-2-yl) benzoic acid (3,7-dimethyloctyl) ester p- (5-hexylpyrimidin-2-yl) benzoic acid (3,7-dimethyloctyl) - p- (5-Pentylpyrimidin-2-yl) benzoic acid (3,7-dimethyloctyl) ester p-fp-dodecyloxyphenyl-1-benzoic acid OJ-dimethyloctyl ester, K59 Sa (52) I p-ip-undecyloxyphenyO- benzoic acid β-dimethyloctyo-O, p-ip-decyloxyphenyll-benzoic acid fS-dimethyloctyo-ester, p-fp-nonyloxyphenyl o-benzoic acid-fSJ-dimethyloctyl-ester, p-fp-octyloxypheny-D-benzoic acid OJ-dimethyloctyl-ester , K45 Sg 48 S _A p -fp-heptyloxy-phenoxy-O-benzoic acid OJ-dimethyloctyl, p-lp-hexyloxyphenyl-benzoic O-dimethyloctyl, p-fp-pentyloxyphenyl O-benzoic acid iso -dimethyloctyo-ester, p-fp-Dodecyloxybenzoyloxy-benzoic acid ISJ-dimethyloctyl (ester p-fp-undecyloxybenzoyloxy-benzoic acid p-fp-decyloxybenzoyloxyJ-benzoic acid iSJ-dimethioctylj-ester p-fp-nonyloxybenzoyloxyj-benzoic acid OJ-dimethyloctylyl ester p- (p-octyloxybenzoyloxy) benzoic acid (3,7-dimethyloctyl) -ester p-fp-heptyloxybenzoyloxybenzoic acid O -dimethyloctyl J-ester p-fp-hexyloxybenzoyloxybenzoic acid O, -dimethyloctylyl ester, K44 S _A p- (p-pentyloxybenzoyloxy) benzoic acid (3,7-dimethyloctyl ) ester p- (trans-4-dodecylcyclohexylbenzoic acid (3,7-dimethyloctyl) ester p- (trans-4-undecylcyclohexylbenzoic acid (3,7-dimethyloctyl) ester p- (trans-4-) Decylcyclohexylbenzoic acid (3,7-dimethyloctyl) ester p-ftrans ^ -nonylcyclohexylbenzoic acid OJ-dimethyloctyl ester p- (trans-4-octylcyclohexylbenzoic acid (3,7-dimethyloctyl) ester p-ftrans ^ -Heptylcyclohexylbenzoic acid fSJ-dimethyloctyl ester, S _B -9I p -ttrans ^ -xyxycyclohexylbenzoic acid OJ-dimethyloctyi) ester p-ltrans ^ -pentylcyclohexylbenzoic acid-fSJ-dimethyloctyo-ester

Example 11:

To a solution of 26.4 g (120 mmol) of 2,6-di-tert-butyl-4-methylphenol in 200 ml of toluene, 30 ml (60 mmol) of a 2 M solution of trimethylaluminum in hexane are added dropwise. The mixture is stirred at room temperature for 1 h and then cooled to -78 ° C. (Journal Am. Chem. Soc., 107, 4573-4576 [1985]). Successively, a solution of 7.6 g (20 mmol) of 4- (4'-octyloxybiphenyl) cyclohexanone in 22 ml of toluene and 38 ml (60 mmol) of a 1.6 ml solution of MeLi in diethyl ether are added dropwise. The mixture is stirred for ² h at -78 ⁰ C and the reaction mixture is added dropwise with ice cooling in 1 M hydrochloric acid. The organic phase is separated off, neutralized with NaHCO 3 solution, dried (Na ₂ SO ₄ ) and chromatographed on neutral aluminum oxide with toluene. Crystallization from ethyl acetate gives the pure 1-methyl-4- (4'-octyloxybiphenyl) cyclohexan-1-ol (20). To a suspension of 0.5 g (15 mmol) NaH (80% in paraffin oil) in 8 ml THF are successively added 4.0 g (15 mmol) of (S) -3,7-dimethyl-1-iodooctane and 3.9 g (10 mmol) (20 ) dissolved in 8 ml of THF. The mixture is stirred for 20 h at 5O ⁰ C, hydrolyzed with saturated NaCl solution, the organic phase is separated and chromatographed with toluene on silica gel. Concentration gives 1-methyl-4- (4'-octyloxybiphenyl-4-yl) -cyclohexyl-1- (3,7-dimethyloctyl) ether.

Example 12:

To a suspension of 0.5 g (15 mmol) of NaH (80% in paraffin oil) in 8 ml of THF are successively added 3.6 g (15 mmol) of 1-iodooctane and 4.2 g (10 mmol) of i-methyl- W -fSJ-dimethyloctyloxy-J-biphenyl α-Cyclocyclohexan-1-ol [Obtainable by etherification of 4'-bromobiphenylol with (S) -3,7-dimethyl-1-iodooctane, reaction with cyclohexanedione monoethylene ketal and MAD as described in Example 11] dissolved in 8 ml of THF. The mixture is stirred at 50 ^° C. for 20 h, worked up as usual, giving 1-methyl-4- [4 '- (3,7-dimethyloctyloxy) -biphenyl-4-yl] -cyclohexyl-1-octyl ether.

Example 13:

42.2 g (100 mmol) of 1-methyl-trans-4- (4'-octyloxybiphenyl) -cyclohexane-1-carboxylic acid (25) (obtainable by saponification of the corresponding carbonitrile compound according to DE-OS 3520115 or the European patent application 85101858.0) are analogous to previous examples, with 15.8 g (100 mmol) of (S) -3,7-dimethyl octanol to give 1-methyl-trans-4- (4'-octyloxybiphenyl-1-cyclohexane-1-carboxylic acid, 3,7-dimethyloctyl esterified analogously: 4- [trans-4- (4-octylcyclohexyl) -cyclohexyl] benzoic acid (3,7-dimethyloctyl) ester.

Example 14:

31.0g (100mmol) of 4'-octyloxybiphenylcarboxaldehyde (obtainable by reduction of the corresponding nitrile with DIBAH), 18.8g (100mmol) of (S) -2- (3,7-dimethyloctyl) -propane-1,3-diol (available by LiAlH ₄ reduction of (S) -2- (3,7-dimethyloctyl) -malonic acid dimethyl ester which is obtainable by reaction of malonate-dimethylester-bis-S-dimethyl-i-iodooctane in methylene chloride / O / NaOH / tetrabutylammonium hydrogensulfate) and 1 , 9g p-Toluolsulfonsäurehydrat are heated in a mixture of 150ml cyclohexane and 15ml petroieumbenzine (boiling range 40-60 ⁰ C) until no more water separates. After customary work-up, chromatography on alumina and crystallization gives optically active trans-2- (4'-octyloxybiphenyl-4-yl) -5- (3,7-dimethyloctyl) -1,3-dioxane.

Example 15:

35.7 g of 2- (4'-octyloxybiphenyl-4-yl) -propane-1,3-diol (obtainable by reaction of 4'-octyloxybiphenyl-4-yl bromide with deprotonated cyanoacetate under Pd (PPh _{3 4} catalysis (J. Chem. Soc. Chem. Commun. 932, 1984), saponification of the nitrile with HCl / ethanol to 35, and reduction with LiAlH ₄ in THf) are obtainable with (S) -2,7-dimethyloctanal (available by reaction of (S) -dihydrocitronellol with pyridinium chlorochromate in methylene chloride) and p-toluenesulfonic acid in cyclohexane / petroleum benzine as described in the preceding example to give optically active trans-5- (4'-ocfyloxybiphenyl-4-yl) -2- (3,7 -dimethyloctyl) -1,3-dioxane reacted.

Example 16:

33.9 g (100 mmol) of 4 '- (3,7-dimethyloctyloxy) -biphenylcarboxaldehyde (obtainable by etherification of 4'-bromobiphenylol with (S) -3,7-dimethyl-1-iodooctane, bromine / cyan exchange and reduction of the Nitriles with DIBAH) are reacted with 2-octylpropane-1,3-diol and p-toluenesulfonic acid as described in the preceding examples to give optically active trans-2- [4 '- (3,7-dimethyloctyloxybiphenyl-4-yl) -5- reacted octyl-1,3-dioxane.

Example 17:

34.7 g (100 mmol) of (S) -1,1,3,3-tetraethoxy-2- (2,6-dimethylheptyl) -propane (obtainable by reacting (S) -3,7-dimethyloctanal with piperidine in the presence of K2CO3 and subsequent reaction of (S) -N- (3,7-dimethyl-1-octenyl) -piperidine with triethyl orthoformate / FeCl) are stirred with 36 ml of ethanol and 2 ml of 5% H ₂ SO ₄ 7h at 40 ⁰ C. Then, this solution is added dropwise to a solution of 24.7 g (220 mmol) of potassium tert-butoxide and 13.8 g of 4-hydroxyphenylamidine · hydrochloride 60 ml of ethanol. Stirred for 3h at room temperature, acidified with conc. Hydrochloric acid, sucks off the precipitated KCl, the lye narrows and brings them to crystallization. The crude crystals are recrystallized from CH ₂ Cl ₂ to give pure p- [5- (2,6-dimethylheptyl) -pyrimidin-2-yl] phenol. Of these, 29.8 g (50 mmol) are added to a suspension of 5 g KOH in 50 ml toluene and 2.1 g polyethylene glycol. At 50 ⁰ C 14.5 g of 1-bromooctane are added dropwise. It is stirred overnight at 50 ° C, worked up as usual and receives 2-p-octyloxyphenyl-5- (2,6-dimethylheptyl) -pyrimidine.

Analog are produced:

2-p-decyloxyphenyl-5- (2,6-dimethylhepty) - pyrimidine

2-p-nonyloxyphenyl-5- (2,6-dimethyihepty) - pyrimidine

2-p-heptyloxyphenyl-5- (2,6-dimethylhepty [) - pyrimidine

2-p-hexyloxyphenyl-5 (2,6-pyrimidin-dimethylheptylJ

2- (4'-Decyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4'-Nonyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4'-Octyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4'-Heptyloxybiphenyl-4-yl) -5- {2,6-dimethylheptyl) -pyrimidine 2- (4 'Hexyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4'-Pentyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyrimidine 2-p-decyloxyphenyl-5 - (3,7-dimethyloctyl) -pyrimidine 2-p-Nonyloxyphenyl-5- (3,7-dimethyloctyl) -pyrimidine 2-p-octyloxyphenyl-5- (3,7-dimethyloctyl) -pyrimidine 2-p-heptyloxyphenyl- 5- (3,7-dimethyloctyl) -pyrimidine 2-p-hexyloxyphenyl-5- (3,7-dimethyloctyl) -pyrimidine 2-p-Pentyloxyphenyl-5- (3,7-dimethyloctyl) -pyrimidine 2-p-decyloxyphenyl -5- (4,8-dimethylnonyl) -pyrimidine 2-p-Nonyloxyphenyl-5- (4,8-dimethylnonyl) -pyrimidine 2-p-octyloxyphenyl-5- (4,8-dimethylnonyl) -pyrimidine 2-p- Heptyloxyphenyl-5- (4,8-dimethylnonyl) -pyrimidine 2-p-Hexyloxyphenyl-5- (4,8-dimethylnonyl) -pyrimidine 2-p-Pentyloxyphenyl-5- (4,8-dimethylnonyl) -pyrimidine 2- ( 4-Decylo xy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-Nonyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-octyloxy-2-) fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-Heptyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-hexyloxy-2-fluorophenyl) -5 - (2,6-dimethylheptyl) -pyrimidine 2- (4-Pentyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-decyloxy-3-fluorophenyl) -5- (2, 6-dimethylheptyl) -pyrimidine 2- (4-Nonyloxy-3-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-Oxyloxy-3-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-Heptyloxy-3-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-hexyloxy-3-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2- (4-pentyloxy-3-fluorophenyl) -5- (2,6-dimethylheptyl) -pyrimidine 2-p-decyloxyphenyl-5- (2 _r 6-dimethylheptyl) -pyridine 2-p-nonyloxyphenyl-5- (2,6 -dimethylheptyl) -pyridine 2-p-Heptyloxyphenyl-5- (2,6-dlmethylheptyl) -pyridine 2-p-hexyloxyphenyl-5- (2,6-dimethylheptyl) -pyridine 2- (4'-Decyloxybiphenyl-4-yl ) -5- (2,6-dimethylheptyl) pyridine 2- (4'-Nonyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyridine 2- (4'-Octyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyridine 2- (4'-Heptyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyridine 2- (4'-Hexyloxybiphenyl-4-yl) -5- (2,6-dimethylheptyl) -pyridine 2- (4 '- Pentyloxybiphenyl-4-yl) -5- (2,6-dim8thylheptyl) -pyridine 2-p-Decyloxyphenyl-5- (3,7-dimethyloctyl) -pyridine 2-p-Nonyloxyphenyl-5- (3,7- dimethyloctyl) -pyridine 2-p-octyloxyphenyl-5- (3,7-dimethyloctyl) -pyridine 2-p-heptyloxyphenyl-5- (3,7-dimethyloctyl) -pyridine 2-p-hepyloxyphenyl-5- (3,7 -dimethylcotyl) -pyridine 2-p-Pentyloxyphenyl-5- (3,7-dimethyloctyl) -pyridine 2-p-decyloxyphenyl-5- (4,8-dimethylnonyl) -pyridine 2-p-nonyloxyphenyl-5- (4, 8-dimethylnonyl) -pyridine 2-p-Octyloxyphenyl-5- (4,8-dimethylnonyl) -pyridine 2-p-Heptyloxyphenyl-5- (4,8-dimethylnonyl) -pyridine 2-p-hexyloxyphenyl-5- (4 , 8-dimethylnonyl) -pyridine 2-p-pentyloxyphenyl-5- (4,8-dimethylnonyl) -pyridine 2- (4-decyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyridine 2- 4-nonyloxy-2-fluorophenyl) -5- (2,6-dimethylhe ptyl) -pyridine 2- (4-Octyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyridine 2- (4-Heptyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyridine 2- (4-Hexyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyridine 2- (4-Pentyloxy-2-fluorophenyl) -5- (2,6-dimethylheptyl) -pyridine 2- (4 Decyloxy-3-fluorophenyl-5- (2,6-dimethylheptyl) -pyridine 2- (4-Nonytoxy-3-fluorophenyl-5- (2,6-dimethylheptyl) -pyridine 2- (4-octyloxy-3 -fluorophenyl-5- (2,6-dimethylheptyl) -pyridine 2- (4-Heptyloxy-3-fluorophenyl-5- (2,6-dimethylheptyl) -pyridine 2- (4-hexyloxy-3-fluorophenyl-5 - 2,6-dimethylheptyl) -pyridine 2- (4-Pentyloxy-3-fluorophenyl-5- (2,6-dimethylheptyl) -pyridine

Example 18:

To a solution of 10.1 g (100 mmol) of diisopropylamine in 100 ml of THF is added dropwise at -10 ° C 62.5ml (lOOmmol) of a 1.6m solution of butyllithium in hexane. The mixture is stirred for 15 minutes at -10 ° C, then cooled to -78 ° Cab and added dropwise a solution of 28.9 g (100 mmol) of trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarbonitrile in 100 ml of THF. The mixture is stirred for 15 min at -78 ⁰ C and then added dropwise 26.8 g of (S) -3,7-dimethyliodoctane at -78 ° Czu. It is stirred at -78 ° C for 3 h. Then allowed to warm to room temperature, poured into 0.51 hydrochloric acid, shaken with toluene and chromatographed with toluene on silica gel. Recrystallization from methanol gives optically active r-1-cyano-cis-4- (trans-4-heptylcyclohexyl) -1- (3,7-dimethyloctyl) -cyclohexane, K45 S ₈ (42)

Example 19:

By reaction of optically active a- (2-methylbutyloxy) -propionic acid chloride (obtainable by reaction of L - (+) - ethyl lactate with optically active 2-methylbutyl iodide in the presence of Ag ₂ O, ester cleavage and conversion into the acid chloride with thionyl chloride) with4- (n-Octyloxy) -4'-hydroxybiphenyl gives 4- (n-octyloxy) -4 '- [α- (2-methylbutyloxy) -propanoxyloxy] biphenyl.

Example 20:

In the dark at 14O ⁰ C in a solution of 6.20g (60mmol) of chlorosulfonic acid and 0.743g (3mmol) of p-chloroanil in 103.36g (600mmol) (S) -3,7-Dimethyloctansäurehür2h a mixture of chlorine and oxygen is introduced , The mixture is allowed to cool to room temperature, taken up in CH ₂ Cl ₂ and shaken out successively with a Na ₂ S2O ₃ solution and water. The organic phase is dried (Na ₂ SCv) and concentrated. After usual work-up, (2R, 2S, 3S) -2-chloro-3,7-dimethyloctanoic acid is obtained.

Example 21:

A solution of 41.34 g (200 mmol) (2R, 2S, 3S) -2-chloro-3,7-dimethyloctanoic acid is added dropwise at ⁰ ° C. under N ₂ to a suspension of 7.96 g (210 mmol) of LiAlH ₄ in 400 ml of ether , The mixture is stirred for 15 minutes and hydrolyzed by dropwise addition of a mixture of 20 ml of water and 80 ml of THF. 600 ml of dilute H ₂ SO _{4 are added} , the organic phase is separated off and the aqueous phase is extracted twice more with ether. The combined organic phase is shaken with a saturated NaHCO ₃ solution, dried (Na ₂ SO ₄ ) and concentrated. After usual work-up, (2R, 2S, 3S) -2-chloro-3,7- is obtained. dimethyl octanol.

Example 22:

To 27.56 g (160 mmol) of (S) -3,7-dimethyloctanoic acid are added with stirring 46.4 ml (640 mmol) of thionyl chloride and then heated to 70 ° C. After 1 h, the mixture is cooled to 20 ⁰ C and gives 42.73 g (320 mmol) of N-chlorosuccinimide and 5 drops of conc. Hydrochloric acid to the solution. The suspension is again heated to 70 ⁰ C. After 1.5 h, the excess thionyl chloride is distilled off (in vacuo), the residue is taken up in 80 ml of CCI ₄ and filtered off from succinimide. After removal of the solvent, (2R, 2S, 3S) -2-chloro-3,7-dimethyloctanoyl chloride is obtained as a light yellow oil.

1 H-NMR (200MHz): 0.80-0.95 (6H, 2d, 2CH ₃ ); 0.97 to 1.16 (3H, 2d, CH _3), 1.16 to 1.66 (7H, m, 3CH ₂ and 1CH); 2.24 to 2.53 (1H, m, CH ₃ CH CHCI); 4.40-4.66 (1H, 2d, CHCHCICOCI).

Example 23:

41.34 g (200 mmol) of (2R, 2S, 3S) -2-chloro-3,7-dimethyloctanoic acid, 59.69 g (200 mmol) of p- (5-nonylpyrimidin-2-yl) -phenol and 2.44 g of 4-N , N'-Dimethylaminopyridine (DMAP) are dissolved in 320 ml of toluene. A solution of 41.27 g of dicyclohexylcarbodiimide (DCC) in 46 ml of toluene is added dropwise, and the mixture is stirred for 20 h. It is filtered with toluene over 1 kg of silica gel and concentrated to dryness. The diastereomer mixture thus obtained is separated by chromatography. The two diastereomers are recrystallized from acetone. There are obtained 2-p - [(2R, 3S) -2-chloro-3,7-dimethyloctanoyloxy] -phenyl-5-nonylpyrimidine and 2-p - [(2S, 3S) -2-chloro-SJ-dimethyloctanoyloxy-phenyl -S-nonylpyrimidine.

Analog are produced:

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-decylpyrimidine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-undecylpyrimidine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-octylpyrimidine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-heptylpyrimidine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-hexylpyrimidine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-decyl pyridine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-undecylpyridin

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-nonylpyridine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-octyl pyridine

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-heptylpyridin

2-p- (2-chloro-3,7-dimethyloctanoyloxy) phenyl-5-hexylpyridine

2 [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-undecylpyridin

2- [4 '- (2-Chloro-3,7-dimethy octanoyloxy!) Biphenyl-4-yl] -5-decyl pyridine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-nonylpyridine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-octyl pyridine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-heptylpyridin

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) -biphenyl-4-yl] -5-hexylpyridine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) -biphenyl-4-yl] -5-undecylpyrirnidine 2- [4' - (2-chloro-3,7-dimethyloctanoyloxy) -biphenyl-4- yl] -5-decylpyrimidine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-nonylpyrimidine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) biphenyl-4-yl] -5-octylpyrimidine

2- [4 '- (2-chloro-3,7-dimethyloctanoyloxy) -biphenyl-4-yl] -5-heptylpyrimidine 2- [4' - (2-chloro-3,7-dimethyloctanoyloxy) -biphenyl-4- yl] -5-hexylpyrimidine

4 '- (2-chloro-3,7-dimethyloctanoyloxy) -4-undecyloxybiphenyl 4' - (2-chloro-3,7-dimethyloctanoyloxy) -4-decyloxybiphenyl 4 '- (2-chloro-3,7-dimethyloctanoyloxy) 4-nonyloxybiphenyl 4 '- (2-chloro-3,7-dimethyloctanoyloxy) -4-octyloxybiphenyl 4' - (2-chloro-3,7-dimethyloctanoyloxy) -4-heptyloxybiphenyl 4 '- (2-chloro-3, 7-dimethyloctanoyloxy) -4-hexyloxybiphenyl p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-undecyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-decyloxyphenyl ester p- (2 -Chloro-3,7-dimethyloctanoyloxy) -benzoic acid p-nonyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-octyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-heptyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-hexyloxyphenyl ester

Example 24:

To a solution of 32.83 g (110 mmol) of p- (5-nonylpyrimidin-2-yl) -phenol, 23.32 g (121 mmol) of (2R, 2S, 3S) -2-chloro-3,7-dimethyloctanol and 28 , 85 g of triphenylphosphine in 270 ml of THF are added dropwise 18.8 ml (121 mmol) of diethyl azodicarboxylate. The mixture is stirred for 18 h at room temperature and then concentrated. Recrystallization from toluene removes the triphenyl phosphine oxide.

The diastereomer mixture is separated by chromatography and the two diastereomers are recrystallized from hexane. There are obtained 2-p - [(2R, 3S) -2-chloro-3,7-dimethyloctyloxy] -phenyl-5-nonylpyrimidine and 2-p - [(2S, 3S) -2-chloro-3,7-dimethyloctyloxy ] phenyl-5-nonylpyrimidine.

Analog are produced:

2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-decylpyrimidine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-undecylpyrimidine 2-p- (2-chloro 3,7-dimethyloctyloxy) -phenyl-5-octylpyrimidine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-heptylpyrimidine 2-p- (2-chloro-3,7-dimethyloctyloxy) - phenyl-5-hexylpyrimidine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-decylpyridine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-undecylpyridine 2-p (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-nonylpyridine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-octylpyridine 2-p- (2-chloro-3, 7-dimethyloctyloxy) -phenyl-5-heptylpyridine 2-p- (2-chloro-3,7-dimethyloctyloxy) -phenyl-5-hexylpyridine

2- [4 '- (2-chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-undecylpyridine -. ,

2- [4 '- (2-chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-decylpyridine 2- [4' - (2-chloro-3,7-dimethyloctyloxy) -biphenyl-4- yl] -5-nonylpyridine 2- [4 '- (2-Chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-octylpyridine 2- [4' - (2-Chloro-3,7-dimethyloctyloxy ) -biphenyl-4-yl] -5-heptylpyridine 2- [4 '- (2-Chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-hexylpyridine 2- [4' - (2-Chloro 3,7-dimethyloctyloxy) biphenyl-4-yl] -5-undecylpyrimidine 2- [4 '- (2-Chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-decylpyrimidine 2- [4 '- (2-chloro-3,7-dimethyloctyloxy) biphenyl-4-yl] -5-nonylpyrimidine 2- [4' - (2-chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5 octylpyrimidine 2- [4 '- (2-chloro-3,7-dimethyloctyloxy) -biphenyl-4-yl] -5-heptylpyrimidine 2- [4' - (2-chloro-3,7-dimethyloctyloxy) -biphenyl- 4-yl] -5-hexylpyrimidine 4 '- (2-chloro-3,7-dimethoyloctyloxy) -4-undecyloxybiphenyl 4' - (2-chloro-3,7-dimethoyloctyloxy) -4-decyloxybiphenyl 4 '- (2- Chloro-3,7-dimethoyloctyloxy) -4-nonyloxybiphenyl 4 '- (2-chloro-3,7-dimethoyloctyloxy) -4-octyloxybiphenyl 4' - (2-chloro-3,7-dimethoxyacty 4-heptyloxybiphenyl 4 '- (2-chloro-3,7-dimethoyloctyloxy) -4-hexyloxybiphenyl p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-undecyloxyphenyl ester p- (2-chloro) 3,7-dimethyloctanoyloxy) -benzoic acid p-decyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) -benzoic acid p-nonyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) benzoic acid p-octyloxyphenyl ester p- (2-Chloro-3,7-dimethyloctanoyloxy) -benzoic acid p-heptyloxyphenyl ester p- (2-chloro-3,7-dimethyloctanoyloxy) -benzoic acid p-hexyloxyphenyl ester

Example 25:

To a solution of 16.2 g of sodium methylate and 0.2 mol of p- (5-n-nonylpyrinnidin-2-yl) -phenol in 150 ml of methanol in the boiling heat 80.5g (S) -3,7-dimethyl-1 -iodoctane dripped. After 5 hours, work up as usual. Optically active 2-p- (3,7-dimethyloctyloxy) -phenyl-5-nonylpyrimidine, K27 S _A 401, is obtained.

Analog are produced:

2-p- (3,7-dimethyloctyoxy) -phenyl-5-pentylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-hexylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl- 5-heptylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-octylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-decylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl 5-undecylpyrimidine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-dodecylpyrimidine

2-p- (3,7-dimethyloctyloxy) -phenyl-5-pentylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-hexylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5- heptylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-octylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-decylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5 -undecylpyridine 2-p- (3,7-dimethyloctyloxy) -phenyl-5-dodecylpyridine 4 '- (3,7-dimethyloctyloxy) -4-pentylbiphenyl 4' - (3,7-dimethyloctyloxy) -4-hexyl- biphenyl 4 '- (3,7-dimethyloctyloxy) -4-heptylbiphenyl 4' - (3,7-dimethyloctyloxy) -4-octylbiphenyl 4 '- (3,7-dimethyloctyloxy) -4-decyl-biphenyl 4 '- (3,7-dimethyloctyloxy) -4-undecyl-biphenyl 4' - (3,7-dimethyloctyloxy) -4-dodecyl-biphenyl 4 '- (3,7-dimethyloctyloxy) -4-pentyloxy-biphenyl 4'- (3,7-dimethyloctyloxy) -4-hexyloxy-biphenyl 4 '- (3,7-dimethyloctyloxy) -4-heptyloxy-biphenyl 4' - (3,7-dimethyloctyloxy) -4-octyloxy-biphenyl 4 '- (3 , 7-dimethyloctyloxy) -4-decyloxybiphenyl 4 '- (3,7-dimethyloctyloxy) -4-undecyloxybiphenyl 4' - (3,7-dimethyloctyloxy) -4-dodecyloxybiphenyl

Example A:

A liquid crystalline phase consisting of 3.3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 3.3% 2-p-heptyloxyphenyl-5-heptylpyrimidine 3.3% 2-p-Nonyloxyphenyl-5-heptylpyrimidine 7.8% 2 -p-hexyloxyphenyl-5-nonylpyrimidine 25.6% 2-p-Nonyloxyphenyl-5-nonylpyrimidine 31.1% r-1-cyano-cis-4- (4'-butyloxybiphenyl-4-yl) -1-octylcyclohexane 15 , 6% of r-1-cyano-cis-4- (4'-heptylbiphenyl-4-yl) -1-hexylcyclohexane 6.7% of r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1 - (trans-4-pentylcyclohexyl) cyclohexane is mixed with 10% of the optically active compounds A, B and C: A: S-methyl ^ -chlorobutyric acid p-fö-n-heptylpyrimidin ^ -ylJ-phenyl ester B: S -Methyl ^ -chloropentanoic acid p-IB-n-heptylpyrimidine ^ -yO-phenyl ester C: 4-Methyl-2-chloropentanoic acid p- (5-n-heptylpyrimidin-2-yl) -phenyl ester The observed phase transition temperatures and the values for the spontaneous polarization at 20 ° are given in the following table:

opt. active S / S _A S _A / Ch Ch / IP _s

connection

A 73 78 95 14.3

B 76 77 85 12.7

C 74 78 95 6.5

Example B:

Prepare a liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine 3% 2-p-octyloxyphenyl-5-heptylpyrimidine 3% 2-p-nonyloxyphenyl 5-heptylpyrimidine 7% 2-p-hexyloxyphenyl-5-nonylpyrimidine 23% 2-p-Nonyloxyphenyl-5-nonylpyrimidine 28% r-1-cyano-cis-4- (4'-butyloxybiphenyl-4-yl) -1- octylcyclohexane 14% r-1-cyano-cis-4- (4'-heptylbiphenyl-4-yl) -1-hexylcyclohexane 6% r-1-cyano-cis-4- (tris-4-pentylcyclohexyl) -1- ( trans-4-pentylcyclohexyl) cyclohexane and 10% 2-chloro-3-methylbutyric acid 4 '- (4-cyano-4-octylcyclohexyl) biphenyl-4-yl ester.

Example C:

A liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine 3% 2-p-octyloxyphenyl-5-heptypyrimidine 3% 2-p-Nonyloxyphenyl-5 -heptylpyrimidine 7% 2-p-hexyloxyphenyl-5-nonylpyrimidine 23% 2-p-Nonyloxyphenyl-5nonylpyrimidine 28% r-1-cyano-cis-4- (4'-butyloxybiphenyl-4-yf) -1-octylcyclohexane 14% r-1-cyan-cis-4- (4'-heptylbiphenyl-4-y!) - 1-hexylcyclohexane

6% of r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1- (trans-4-pentylcyclohexyl) cyclohexane and 10% of 4,4'-bis (2-chloro-3-methylbutyryfoxy) biphenyl has a spontaneous potential of 38nC / cm ² at room temperature and an Sf / Ch conversion at 68 °.

254

Example D:

A liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine 3% 2-p-Octyloxyphenyl-5-heptylpyrimidine 3% 2-p-Nonyloxyphenyl-5-heptylpyrimidine 7% 2-p-hexyloxyphenyl-5-nonylpyrimidine 23% 2-p-Nonyloxyphenyl-5-nonylpyrimidine 28% r-1-cyano-cis-4- (4'-butyloxybiphenyl-4-yl) -1-octylcyclohexane 14% r-1-cyano-cis-4- (4'-heptylbiphenyl-4-yl) -1-hexylcyclohexane 6% r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1- {trans-4 -pentylcyclohexyl) -cyclohexane and IC ^ / oS-MethyW-chlorobutyric acid p-IB-n-octylpyridine ^ -d-phenylester has a spontaneous polarization of lenC / cm ² at room temperature.

Example E:

A liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine 3% 2-p-octyloxyphenyl-5-heptylpyrimidine 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine 7% 2-p-hexyloxyphenyl-5-nonylpyrimidine 23% 2-p-Nonyloxyphenyl-5-nonylpyrimidine 28% r-1-cyano-cis-4- (4'-butyloxybiphenyl-4-yl) -1-octylcyclohexane 14% r-1-cyano-cis-4- (4'-heptylbiphenyl-4-yl) -1-hexylcyclohexane 6% r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1- (trans-4 -pentylcyclohexyl) -cyclohexane and K ^ / oS-methyl ^ -chlorinazenoic acid p-fB-n-octylpyridine ^ -d-phenyl ester has a spontaneous polarization of 19nC / cm ² at room temperature.

Example F:

A liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine, 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine, 3% 2-p-octyloxyphenyl-5-heptylpyrimidine, 3% 2-p-nonyloxyphenyl 5-heptylpyrimidine, 6% 2-p-hexyloxyphenyl-5-nonylpyrimidine, 25% 2-p-nonyloxyphenyl-5-nonylpyrimidine, 3% r-1-cyano-cis-4- [4'-trans-4-pentylcyclohexyl) -biphenyl-4-yl] -1-pentylcyclohexane, 15% r-1-cyano-cis-4- (4'-octyloxybiphenyl-4-yl) -1-nonylcyclohexane 15% r-1-cyano-cis-4 (4'-octyloxybiphenyl-4-yl) -1-octylcyclohexane 10% 2-Chloro-3-methylbutanoic acid [4 '- (4-cyano-4-octylcyclohexyl) biphenyl-4-yl] ester (optically active ), 6% r-1-cyano-cis-4- (4'-heptyloxybiphenyl-4-yl) -1- (2-methylbutyl) -cyclohexane (optically active) and 8% r-1-cyano-cis-4 - [4 '- (7-cyano-octyloxy) -biphenyl-4-yl] -1-hexy-cyclohexane (optically active) shows S? / S _A 60 °, S _A / Ch 63 °, Ch / I 84 ° and P ₃ = 20nC / cm ² .

Example G:

A liquid crystalline phase consisting of 3% 2-p-hexyloxyphenyl-5-heptylpyrimidine, 3% 2-p-heptyloxyphenyl-5-heptylpyrimidine, 3% 2-p-octyloxyphenyl-5-heptylpyrimidine, 3% 2-p-nonyloxyphenyl 5-nony (pyrimidine, 3% 2-p-heptyloxyphenyl-5-nonylpyridine, 3% 2-p-octyloxyphenyl-5-nonylpyridine, 25% 2-p-nonyloxyphenyl-5-nonylpyrimidine, 15% r-1-cyano cis -4- (4'-octyloxybiphenyl-4-yl) -1-octylcyclohexane, 5% p- (4-cyano-4-heptylcyclohexyl) -benzoic acid p-heptyl-phenyl ester, 5% r-1-cyano-cis 4-pentylcyclohexanecarboxylic acid p- (trans-4-propylcyclohexyl) phenyl ester, 5% r-1-cyano-cis-4- (4'-hexylbiphenyl-4-yl) -1-heptylcyclohexane and 12% 2-chloro 3-methylbutyric acid p- (5-nonylpyridin-2-yl) -phenyl ester (optically active) shows S? / Sa 61 °, S _A / Ch 64 °, Ch / I 82 ° and P _s = 16nC / cm ² .

Claims (2)

1. chiral tutted smectic liquid-crystalline phase having at least two liquid-crystalline components, characterized in that it comprises at least one optically active compound of the formula 1 _R i_Qi_C * HX-Q ² -A ⁴ -Z ¹ -A ² - (Z ² -A ³ ) _n -R ² I R ¹ and R ² each represent a straight-chain or branched alkyl or perfluoroalkyl group each having 1-12 C atoms, in which also one or more CH ₂ or CF ₂ groups is represented by a grouping selected from the group-0-, -S-, -CO-, 0-C0-, -O-COO-, -CO-O-, -CH = CH-, -CHHalogen- and -CHCN- or may also be replaced by a combination of two suitable groupings where two heteroatoms are not directly linked to each other, one of the groups R ¹ and R ^{2 is} also F, Cl, Br or CN and R ² and H, A ² , A ³ and A ^{4 are} each unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups substituted 1,4-phenylene, wherein also one or two CH- May be replaced by N, 1,4-cyclohexylene, wherein also one or two non-adjacent CH ₂ groups may be replaced by 0 atoms and / or S atoms, piperidine-1,4-diyl, 1,4- Bicyclo (2,2,2) -octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups, Z ¹ and Z ^{2 are} each -CO-O-, -O-C0-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -C = C- or a single bond, X is halogen, CN or CH ₃ , η O or 1, Q ¹ denotes a single bond or alkylene having 1 to 3 C atoms, in which also a CH ₂ group is represented by -O-, -CO-, -O-C0-, -CO-O-, -CH = CH-COO-, -CH = CH-, -CHHalogen- and / or -CHCN- may be replaced, and Q ² alkylene having 1 to 6 C atoms, in which also one or two CH ₂ groups are denoted by -O-, -CO-, -O-CO-, -CO-O-, -CH = CH-COO-, - CH = CH-, -CHHalogen and / or -CHCN-may be substituted, wherein two heteroatoms are not directly linked together, above a single bond, with the provisos that (a) R ^ Q ^{1 is} a group having at least one branch, and (b) XCH ₃ and / or R ¹ -Q ^{1 is} a group having at least two branches if -A ⁴ -Z ¹ -A ² -R ² 4'-alkoxybiphenyl-4-yl and Q ² -CO- O- means contains. 2. Use of the compound of formula I according to claim 1, characterized in that they are used as components of liquid-crystalline phases.