EP0334925A1 - Ferroelectric liquid crystalline phases - Google Patents

Abstract

The invention relates to the use of compounds of the formula (I): R¹- (CO) mS-aryl-Z¹- (A¹-Z²) n-A²-R², wherein R¹, R², aryl, Z¹, Z², A¹, A², m and n have the meaning given in claim 1, as components of ferroelectric liquid-crystalline phases, and also compounds of the formula (I) and processes for their preparation. Abstract compounds having the formula (I): R¹- (CO) mS-aryl-Z¹- (A¹-R²) n-A²-R², in which R¹, R², aryl, Z¹, Z², A¹, A², m and n have the meaning defined in claim 1 are used as components of ferroelectric liquid crystalline phases. The invention also concerns compounds having the formula (I) and the process for manufacturing them.

Description

 Ferroelectric liquid crystalline phases

The invention relates to the use of compounds of the formula I

R ¹ - (CO) _m -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² I

wherein

R ¹ and R ^{2 are} each independently an unsubstituted or with -CN or with at least one

Halogen substituted alkyl or alkenyl radical with up to 18 carbon atoms, in which one or more CH ₂ groups can be replaced by one

Rest selected from the group -O-, -S-, -CO-,

-O-CO-, -CO-O-, -O-CO-O- and -C≡C-, where 2 heteroatoms are not adjacent, R ² also H, F, Cl, Br, CN or CF ₃ ,

Aryl unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl , Pyrazine-2,5 diyl or pyridazine-3,6-diyl,

Z ¹ and Z ² each -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CH ₂ CH ₂ -,

-OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, or a single bond, A ¹ and A ² each independently

a) a 1,4-phenylene radical, in which one or two CH groups can be replaced by N.

b) a 1,4-cyclohexylene radical, in which one or two non-adjacent CH ₂ groups can be replaced by -O- or -S-.

c) a 1,4-cyclohexenylene, a 1,4-bicyclo [2,2,2] octylene, a naphthalene-2,6-diyl, a decahydronaphthalene-2,6-diyl, a 1 , 2,3,4-tetrahydronaphthalene-2,6-diyl or a piperidine-1,4-diyl radical,

where the radicals a) and b) can be substituted one or more times by halogen atoms, cyano and / or methyl groups,

m 0 or 1, and

n 0, 1 or 2

means, where n = 2 the A ¹ or Z ² radicals can be the same or different from one another, with the proviso that for optically active compounds of the formula I in which n is 0, m = 0 and A ² 1,4-phenylene or 1,4-cyclohexylene which is unsubstituted or substituted once or twice by F, Cl, CH ₃ and / or CN, and one or two of which are not adjacent

CH ₂ groups can be replaced by -O- and / or -S-, means as components of ferroelectric liquid-crystalline phases. For the sake of simplicity, Phe in the following means a 1,4-phenylene group, Cy a trans-1,4-cyclohexylene group, Che a 1,4-cyclohexenylene group, the double bond being both 1,2- and 2,3- and 3,4 may be pyr, a pyridine-2,5-diyl group, Pyz a pyrazine-2,5-diyl group, Pyn a pyridazine-3, 6-diyl group and Pyd a pyrimidine-2,5-diyl group, both of which are regioisomers permitted are.

PheX means a group of the formula where X hereinafter means chlorine, fluorine, methyl or nitrile, preferably X means chlorine or fluorine, particularly preferably fluorine.

Chiral-chopped smectic liquid-crystalline phases with ferroelectric properties can be produced by adding a suitable chiral dopant to basic mixtures with one or more chopped smectic phases (LA Beresnev et al., Mol. Cryst. Lig. Cryst. 89, 327 ( 1982); HR Brand et al., J. Physigue 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 (NA Clark and ST Lagerwall, Appl. Phys. Lett. 36, 899 (1980); USP 4,367,924) on the basis of the ferroelectric properties of the chiral-tinted phase. In this phase, the elongate molecules are arranged in layers, the molecules being one As the layer progresses from layer to layer, the tilt direction changes by a small angle with respect to an axis perpendicular to the layers so that a helical structure is formed. The smekti are in displays based on the principle of SSFLC technology see layers arranged perpendicular to the plates of the cell. The helical arrangement of the tilt directions of the molecules is suppressed by a very small distance between the plates (approx. 1 - 2 μm). This forces the long axes of the molecules to line up in a plane parallel to the plates of the cell, creating two excellent tilt orientations. By applying a suitable electrical alternating field, it is possible to switch back and forth between these two states in the liquid-crystalline phase which has a spontaneous polarization. This switching process is much faster than with conventional twisted cells (TN-LCD's), which are based on nematic liquid crystals.

A major disadvantage for many applications of the currently available materials with chirally smectic phases (such as Sc *, but also S _H *, S _I *, S _J *, S _K *, S _G *, S _F *) is their minor chemical, thermal and photo stability. Another disadvantageous property of displays based on currently available chiral-smectic mixtures is that the spontaneous polarization has values that are too small, so that the switching time behavior of the displays is adversely affected and / or the pitch and / or the tilt and / or the viscosity of the phases not the requirements of

Corresponds to display technology. In addition, the temperature range of the ferroelectric phases is usually too small and is predominantly at too high temperatures.

It has now been found that the use of compounds of the formula I as components of chirally put smectic mixtures can substantially reduce the disadvantages mentioned. The compounds of the formula I are therefore particularly suitable as components of chiral-tipped smectic liquid-crystalline phases. In particular With their help, chemically particularly stable chiral-smotty liquid-crystalline phases with favorable ferroelectric phase ranges, favorable widths for the viscosity, in particular with wide Sc * phase ranges, excellent supercoolability down to temperatures below 0 ° C. without crystallization and for such phases high values for the spontaneous polarization. P is the spontaneous

Polarization in nC / cm ² .

The compounds of formula I have a wide range

Scope of application. Depending on the selection of the substituents, these compounds can serve as base materials from which liquid-crystalline smectic 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 to improve the dielectric and / or optical anisotropy and / or the viscosity and / or the spontaneous polarization and / or the phase ranges and / or the tilt angle and / or the To vary the pitch of such a dielectric.

Some of the compounds of the formula I are known as components of nematic liquid-crystalline phases; some of the compounds of formula I are still new. WO 86-00245 already describes optically active 2- [4-alkylmercap-tophenyl] -5-alkylpyrimidines as dopants for ferroelectric liquid-crystalline phases. Furthermore, US Pat. No. 4,613,209 claims optically active 4-n-alkoxy-4'-alkylthiocarbonyl- or 4-n-alkoxy-4-alkylcarbonylthio-biphenyls in a speculative formula. However, these compounds do not allow the development of modern ferroelectric mixtures because they do not meet today's requirements with regard to their spontaneous polarization and mesogenicity. WO 86-00234 specifies a very broad general formula containing achiral heterocycles for ferroelectric mixtures, which in part comprises the compounds of the formula I claimed here. In WO 86-00234, however, no individual compounds of the formula claimed here are mentioned. The person skilled in the art could therefore neither easily derive synthesis possibilities for the claimed compounds from the prior art nor recognize that the compounds according to the invention predominantly have broad and favorably located Sc phases and are distinguished by favorable values for the rotational viscosity.

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

R ¹ - (CO) _m -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² I '

wherein R ¹ and R ^{2 are} each independently an unsubstituted or with -CN or with at least one halogen substituted alkyl or alkenyl radical with up to

18 carbon atoms, in which one or more CH ₂ groups can be replaced by a radical selected from the group -O-, -S-, -CO-, -O-CO-, -CO-O-, -O -CO-O- and -C≡C-, where 2 heteroatoms are not adjacent, R ² also F, Cl, Br, OH, SH or CN, R ¹ also H, aryl unsubstituted or by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups substituted 1,4-phenylene, Ä ¹ and A ² unsubstituted or once or twice by

F, Cl, CH ₃ and / or CN substituted 1,4-phenylene, Z ¹ denotes a single bond, and Z ² , m and n have the meaning given, with the proviso that when n = 0 R ^{2 is} an alkoxy , Alkylthio, alkoxycarbonyl, Alkanoyloxy or perfluoroalkyl group each having 1-12 C atoms, in which one or more CH ₂ or CF ₂ groups are also selected by a group from the group -O-, -S-, -CO-, -O-CO- , -S-CO-, -O-COO-, -CO-O-, -CO-S-, -CH = CH-, C (CH ₃ ) = CH-, -CH = (CH ₃ ) -, - CHHalogen- and CH-CN- or can be replaced by a combination of two suitable groupings, two heteroatoms not being directly linked, F, Cl, Br, OH, SH or CN, and / or one of the rings aryl or A ² 1,4-phenylene substituted by F, Cl, CH ₃ and / or CN.

The invention furthermore relates to a process for the preparation of the new compounds of the formula I ', characterized in that p-lithium, p-bromomagnesium or p-trialkoxytitanium (alkylthio) aryl compounds are reacted with aldehydes, ketones or nitriles , or that compounds of formula II,

X-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² II

wherein

XN ⁺ ₂ , Cl, Br or J means -and

Aryl, A ¹ , A ² , Z ¹ , Z ² , R ² and n have the meaning given, with alkyl or alkanoyl thiolate compounds of the formula III,

R ¹ - (CO) _m -SM III

in which R ¹ and m have the meaning given, and M denotes a monovalent metal, or in that compound of the formula II, wherein

X SH means and

Aryl, A ¹ , A ² , Z ¹ , Z ² , R ² and n have the meaning given, reacted with alkenes or ketenes,

or that a compound which otherwise corresponds to the formula I 'but contains one or more reducible groups and / or CC bonds instead of H atoms and / or a sulfoxide group instead of a mercapto group, with a reducing group Treated means

or that for the preparation of esters or thioesters of the formula I '(in which m = 1 and / or R ¹ or R ^{2 contains} a carboxyl or thiocarboxyl group and / or Z ¹ or Z ² -CO-O-, -CO-S -, -O-CO- or -S-CO-) react a corresponding carboxylic acid or one of its reactive derivatives with a corresponding alcohol, thiol or its reactive derivatives,

or that for the preparation of ethers or thioethers of the formula I '(in which R ¹ or R ^{2 is} an alkoxy, oxaalkyl or thioalkyl group and / or m = O and / or Z ¹ or Z ² -OCH ₂ -, -CH ₂ O-, -SCH ₂ - or -CH ₂ S-) etherifies a corresponding hydroxyl or sulfhydryl group.

The invention further relates to ferroelectric liquid-crystalline phases containing at least one compound of the formula I and liquid-crystal display elements, in particular ferroelectric electro-optical display elements which contain such phases. The phases according to the invention preferably contain at least two, in particular at least three, compounds of the formula I. Particularly preferred are chiral tilted smectic liquid-crystalline phases according to the invention, the achiral base mixture of which, in addition to compounds of the formula I, contains at least one other component with a negative or small positive dielectric anisotropy. These further component (s) of the achiral base mixture can make up 1 to 50%, preferably 10 to 25%, of the base mixture. Compounds of the formula IV which comprise the compounds of the sub-formulas IVa to IVi are suitable as further components with small positive or negative dielectric anisotropy:

R ⁴ and R ⁵ are each preferably straight-chain alkyl,

Alkoxy, alkanoyloxy or alkoxycarbonyl, each with 3 to 12 carbon atoms. X is preferably 0. In the compounds of the formulas IVa, IVb, IVd, IVe, IVf and IVg, a 1,4-phenylene group can also be substituted laterally by halogen or CN, particularly preferably by fluorine.

Particularly preferred are the compounds of the sub-formulas IVa, IVb, IVd and IVf, in which R ⁴ and R ⁵ each represent straight-chain alkyl or alkoxy each having 5 to 10 carbon atoms.

Particularly preferred individual compounds are given in Table I below:

Table I

Formula R ⁴ R ⁵ X

IVa n-decyloxy n-heptyloxy 0

IVa n-hexyloxy n-decyloxy 0

IVa n-octyloxy n-heptyl 0

IVa n-octyloxy n-pentyl 0

IVa n-decyloxy n-heptyl 0

IVa n-decyloxy n-pentyl 0

IVf n-pentyl n-pentyl 0

IVf n-pentyl n-hexyl 0 The compounds of the sub-formulas IVc, IVh and IVi are suitable as additives for lowering the melting point and are normally added to the base mixtures in an amount of not more than 5%, preferably 1 to 3%. R ⁴ and R ⁵ in the compounds of the sub-formulas IVc, IVh and IVi are preferably straight-chain alkyl having 2 to 7, preferably 3 to 5, carbon atoms. Another class of compounds suitable for lowering the melting point in the phases according to the invention is that of the formula

wherein R ⁴ and R ^{5 have} the preferred meaning given for IVc, IVh and IVi.

Compounds containing the structural element A, B or C are furthermore suitable as further components with negative dielectric anisotropy.

Preferred compounds of this type correspond to the form Va, Vb and Vc:

R ¹ and R ″ each preferably represent straight-chain

Alkyl or alkoxy groups, each with 2 to 10 carbon atoms. Q ¹ and Q ² each represent 1,4-phenylene, trans-1,4-cyclohexylene, 4,4'-biphenylyl, 4- (trans-4-cyclohexyl) phenyl, trans, trans-4,4'-bicyclohexyl or one of the groups Q ¹ and Q ² also a simple formation. Q ³ and Q ⁴ each represent 1,4-phenylene, 4,4'-biphenylyl or trans-1,4-cyclohexylene. One of the groups Q ³ and Q ⁴ can also mean 1,4-phenylene, in which at least one CH group has been replaced by N. R '''is an optically active residue with an asymmetric carbon atom

the structure or Particularly preferred compounds of the formula Vc are those of the formula Vc ':

wherein A is 1,4-phenylene or trans-1,4-cyclohexylene and n is 0 or 1.

The compounds of formula I include dinuclear (n = 0) and trinuclear (n = 1) and ternary (n = 2) materials. Of the dinuclear, those are preferred in which R ^{1 is} n-alkyl having 7 to 12, in particular 7 to 10, carbon atoms. Compounds of the formula I with R ¹ = n-heptyl or n-octyl impart good low-temperature behavior to the phases according to the invention, while the corresponding compounds with R ¹ = n-nonyl are able to increase the S _A / S _C transition temperature of the phases according to the invention. Preferred phases according to the invention contain at least one compound of the formula I in which aryl denotes unsubstituted or substituted 1,4-phenylene. Those compounds of the formula I in which aryl is pyridine or pyrimidine are further preferred.

Binuclear compounds of the formula I accordingly comprise compounds of the sub-formulas Ia to It:

R ¹ -S-Phe-A ² -R ² Ia

R ¹ -CO-S-Phe-A ² -R ² Ib R ¹ -S-PheX-A ² -R ² Ic

R ¹ -CO-S-PheX-A ² -R ² Id

R ¹ -S-Pyd-A ² -R ² Ie

R ¹ -CO-S-Pyd-A ² -R ² If R ¹ -S-Phe-Z ¹ -A ² -R ² Ig R ¹ -CO-S-Phe-Z ¹ -A ² -R ² Ih

R ¹ -S-PheX-Z ¹ -A ² -R ² Ii

R ¹ -CO-S-PheX-Z ¹ -A ² -R ² Ij

R ¹ -S-Pyd-Z ¹ -A ² -R ² Ik

R ¹ -CO-S-Pyd-Z ¹ -A ² -R ² II R ¹ -S-Pyr-A ² -R ² Im

R ¹ -CO-S-Pyr-A ² -R ² In R ¹ -S-Pyr-Z ¹ -A ² -R ² Io

R ¹ -CO-S-Pyr-Z ¹ -A ² -R ² Ip

R ¹ -S-Pyn-A ² -R ² Ig R ¹ -S-Pyn-Z ¹ -A ² -R ² Ir

R ¹ -S-Pyz-A ² -R ² Is

R ¹ -S-Pyz-Z ¹ -A ² -R ² It

Those compounds of the formulas Ia-It in which aryl denotes unsubstituted 1,4-phenylene are very particularly preferred. A ² in the formula Ia-It is preferably unsubstituted ized or substituted 1,4-phenylene or 1,4-cyclohexylene. Those compounds of the form melts Ia-It in which A ^{2 is} unsubstituted 1,4-phenylene are particularly preferred.

Further preferred compounds of the formula I are those of the formula I "

R ¹ - (CO) _ιn -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² I "

wherein R ¹ , R ² , aryl, A ¹ , A ² , Z ¹ , Z ² m and n the at.

Formula I have the meaning given, with the provisos that

a) n 2 if R ^{1 is} branched and aryl means unsubstituted or substituted 1,4-phenylene, and

b) aryl means pyridine-2, 5-diyl or pyrimidine-2, 5-diyl or the group linked to Z ¹ 1,4-phenylene, in which one or two CH groups are replaced by N.

Particularly preferred smaller groups of compounds are those of the formulas I "1 to I" 22

R ¹ -S-Pyd-Phe-R ² I "1

R ¹ -CO-S-Pyd-Phe-R ² I "2

R ¹ -S-Pyr-Phe-R ² I "3

R ¹ -CO-S-Pyr-Phe-R ² I "4

R ¹ -S-Phe-Pyr-R ² I "5

R ¹ -CO-S-Phe-Pyr-R ² I "6

R ¹ -CO-S-Phe-Pyd-R ² I "7

R ¹ -S-Phe-Pyd-R ² I "8

R ¹ -S-Phe-Z ¹ -Pyr-R ² I "9 R ¹ -S-Phs-Z ¹ -Pyd-R ² I "10

R ¹ -S-Pyd-Phe-Phe-R ² I "11 R ¹ -S-Pyr-Phe-Phe-R ² I" 12 R ¹ -S-Pyr-Z ¹ -Phe-Phe-R ² I " 13 R ¹ -S-Pyd-Z ¹ -Phe-Phe-R ² I "14 R ¹ -S-Phe-Pyr-Phe-R ² I" 15 R ¹ -S-Phe-Pyd-Phe-R ² I "16 R ¹ -S-Phe-Z ¹ -Pyr-Phe-R ² I" 17 R ¹ -S-Phe-Z ¹ -Pyd-Phe-R ² I "18

R ¹ -S-Phe-Pyr-Phe-Phe-R ² I "19 R ¹ -S-Phe-Pyd-Phe-Phe-R ² I" 20 R ¹ -S-Phe-Pyr-Z ² -Phe- Phe-R ² I "21 R ¹ -S-Phe-Pyz-Z ² -Phe-Phe-R ² I" 22

Preferred compounds of the formula I are those in which R ¹ and R ^{2 are} each straight-chain or branched

Alkyl or perfluoroalkyl group each having 4-13 C atoms, in which one or two CH ₂ or CF ₂ groups are selected by a group from -O-, -S-, -O-CO-, -CO -O-, -CH = CH-, -CH-halogen and -CHCN- can be replaced, two heteroatoms not being directly linked to one another.

Compounds of the formula I in which R ^{2 is} F, Cl or CN are particularly preferred.

Of the compounds of the formula I in which R ¹ and R ^{2 are} alkyl, in which one or two CH ₂ groups are denoted by —O—,

-S-, -O-CO-, -CO-O-, -CH-halogen and -CHCN- are preferred in which only one CH ₂ group is replaced.

Of these in turn, those are particularly preferred in which, in the case of R ¹ , the methylene group adjacent to the group - (CO) -S- is replaced by -CH-halogen- or -CH-CN-, or in the case of R ² the the group -A ² - neighboring

Methylene group is replaced by -O-, -S-, -CO-O- -O-CO-. Preferred phases according to the invention contain at least one compound of the formula I in which R ^{1 is} n-nonyl and at least one compound of the formula I in which R ^{1 is} n-heptyl or n-octyl. Phases according to the invention containing compounds of the formula I in which R ^{1 is} n-heptyl, n-octyl and n-nonyl are particularly preferred. R ² in the dinuclear (n = 0) compounds of the formula I is preferably n-alkyl, n-alkoxy or n-alkylthio with 6 to 12, in particular with 7 to 10, carbon atoms. The phases according to the invention preferably contain at least one compound of the formula I in which R ^{2 is} n-hexyl, n-heptyl, n-octyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-hexylthio, n-heptylthio, octylthio, n -Hexyl, n-heptyl, n-octyl, (preferably n-hexyl, n-heptyl, n-octyl, n-heptyloxy, n-octyloxy, n-heptylthio or n-octylthio) and at least one compound of the formula I, wherein R ^{2 is} n-nonyl, n-decyl, n-nonyloxy, n-decyloxy, n-nonylthio or n-decylthio.

The sum of the C atoms in the groups R ¹ and R ^{2 of} the preferred dinuclear compounds of the formula I is preferably 15 or higher, particularly preferably in the range from 15 to 20. Particularly preferred individual compounds of the formula I are in the following Table II (aryl) preferably substituted or unsubstituted 1,4-phenylene):

Table II

R ¹ - (CO) _m -S-aryl-A ² -R ²

R ¹ m R ² A ² n-nonyl 0 n-nonyl Phe n-nonyl 0 n-hexyl Phe n-octyl 0 n-decyl Phe R ¹ m R ² A ² n-octyl 0 n-octyl Phe n-octyl 0 n-heptyl Phe n-heptyl 0 n-decyl Phe n-heptyl 0 n-nonyl Phe n-pentyl 1 n-octyl Phe n-hexyl 1 n-Hexyl Phe n-Hexyl 1 n-Pentyl Phe n-Pentyl 1 n-Nonyl Phe n-Octyl 1 n-Octyl Phe n-Nonyl 0 n-Nonyloxy Phe n-Nonyl 0 n-Hexyloxy Phe n-Octyl 0 n -Decyloxy Phe n-octyl 0 n-octyloxy Phe n-octyl 0 n-heptyloxy Phe n-heptyl 0 n-decyloxy Phe n-heptyl 0 n-nonyloxy Phe n-pentyl 1 n-octyloxy Phe n-hexyl 1 n-hexyloxy Phe n-hexyl 1 n-pentyloxy Phe n-pentyl 1 n-nonyloxy Phe n-octyl 1 n-octyloxy Phe n-nonyl 0 n-nonylthio Phe n-nonyl 0 n-hexylthio Phe n-octyl 0 n-decylthio Phe n -Octyl 0 n-octylthio Phe R ¹ m R ² A ² n-octyl 0 n-heptylthio Phe n-heptyl 0 n-decylthio Phe n-heptyl 0 n-nonylthio Phe n-pentyl 1 n-octylthio Phe n-hexyl 1 n-hexyl Phe n-hexyl 1 n-pentylthio Phe n-pentyl 1 n-nonylthio Phe n-octyl 1 n-octylthio Phe n-octyl 0 ethyloxycarbonyl Che n-octyl 0 ethyloxycarbonyl Phe n-octyl 0 nonyl cy n-octyl 0 nonyloxy cy n-octyl 0 nonylthio Cy

Preference is furthermore given to phases according to the invention comprising at least one dinuclear compound of the formula I in which R ^{1 is} n-alkyl having 7 to 10 C atoms and R ²

-CH ₂ O- (CH ₂ ) p-CH ₃ or -O- (CH ₂ ) qO- (CH ₂ ) r-CH ₃ . p is preferably 4 to 10, in particular 5 to 9. q is preferably 1 or 2, particularly preferably 2. r is 4 to 10, particularly preferably 5 to 9. g can also be> 2, for example 3 to 5.

Also preferred are compounds of the formula I in which R ^{1 is} n-alkyl having 7 to 10 carbon atoms and R ^{2 is} n-alkanoyloxy or n-alkoxycarbonyl each having 5 to

10 carbon atoms. The phases according to the invention preferably contain at least one trinuclear compound of the formula I These phases are distinguished by particularly high S _C / S _A conversion temperatures.

Trinuclear compounds of the formula I accordingly comprise compounds of the sub-formulas IA to IP:

R ¹ -S-Phe-A ¹ -A ² -R ² IA

R ¹ -CO-S-Phe-A ¹ -A ² -R ² IB

R ¹ -S-PheX-A ¹ -A ² -R ² IC R ¹ -CO-S-PheX-A ¹ -A ² -R ² ID

R ¹ -S-Phe-Z ² -A ¹ -A ² -R ² IU

R ¹ -S-Phe-A ¹ -Z ¹ -A ² -R ² IF

R ¹ -CO-S-Phe-Z ¹ -A ¹ -A ² -R ² IG

R ¹ -CO-S-Phe-A ¹ -Z ² -A ² -R ² IH R ¹ -S-Phe-Z ¹ -A ¹ -Z ² -A ² -R ² . II

R ¹ -CO-S-Phe-Z ¹ -A ¹ -Z ² -A ² -R ² IJ

R ¹ -S-Pyd-A ¹ -A ² -R ² IK

R ¹ -S-Pyd-Z ¹ -A ¹ -A ² -R ² IL

R ¹ -S-Pyd-Z ¹ -A ¹ -Z ² -A ² -R ² IM R ¹ -S-Pyr-A ¹ -Z ² -A ² -R ² IN

R ¹ -S-Pyn-A ¹ -Z ¹ -A ² -R ² IO

R ¹ -S-Pyz-A ¹ -Z ² -A ² -R ² IP

R ¹ and R ² are each independently of one another preferably alkyl, alkoxy, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy, each preferably having 5 to 12, in particular 6 to 10, carbon atoms. Alkyl and alkoxy are particularly preferred. One of the groups R ¹ and R ² is preferably alkyl. A particularly preferred combination is R ¹ = alkyl and R ² = alkoxy and also R ¹ = alkyl and R ² = alkyl. R ¹ and R ² groups with a straight-chain alkyl radical are particularly preferred. In the trinuclear compounds of the formulas IA to IP, A ¹ and A ^{2 are} preferably unsubstituted or substituted 1,4-phenylene, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl.

The structural element - (A ¹ -Z ² ) _n -A ² - means the partial structural elements 1 to 9 in the case of trinuclear compounds (n = 1):

Phe-Phe 1

PheX-Phe 2 Phe-CO-O-Phe 3

Phe-Cy 4

PheX-Cy 5

Phe-CO-O-Pyr 6

PhöX-CO-O-Cy 7 Pyd-Phe 8

Pyd-PheX 9

In the case of the tetranuclear compounds of the formula I, the compounds of the formulas IQ to IT are preferred:

R ¹ -S-Phe- (A ¹ -Z ² ) ₂ -A ² -R ² IQ R ¹ -S-Pyr- (A ¹ -Z ² ) ₂ -A ² -R ² IR

R ¹ -S-CO-Phe- (A ¹ -Z ² ) ₂ -A ² -R ² IT

wherein the structural element - (A ¹ -Z ² ) ₂ -A ² - preferably the

Substructure elements 10 to 18:

Phe-Phe-Phe 10 Phe-CO-O-Phe-Phe 11

Phe-Phe-CO-O-Phe 12

Phe-Phe-PheX 13

Phe-Phe-Cy 14 Phe-CO-O-Phe-Cy 15

Phe-CO-O-Phe-PheX 16

Pyd-Phe-Phe 17

Pyd-Phe-CO-O-Phe 18

means.

In the compounds of the formulas IA-IT, which contain structural elements 2, 5, 7, 9, 13 and 16 with a group PheX, PheX preferably means a 2- (or 3-) - monofluoro- or 2,3-difluoro- 1,4-phenylene group.

A ferroelectric liquid-crystalline phase with at least one compound of the formula I is particularly preferred, characterized in that it contains a liquid-crystalline component with negative dielectric anisotropy; in particular a phase according to the invention, characterized in that it contains at least one compound having the structural element A, B, C or D as component with negative dielectric anisotropy.

Such compounds of the formula I containing the structural elements A to D are preferably those of the partial forms in Iaa to Ian:

In the chiral compounds of the formulas laa to Ian, a Phe group can each be substituted by one or two fluorine atoms.

Ferroelectric liquid-crystalline phases are preferred which have at least one compound of the formula I with unbranched radicals R ¹ and R ² as the base material and additionally at least one compound of the formulas laa-las with branched, optically active wing groups R ¹ or R ² as dopants.

Those chirally tilted smectic phases which contain at least one compound of the formula I with straight-chain wing groups R ¹ and R ² and are doped with other chiral compounds are particularly preferred.

A phase according to the invention is furthermore particularly preferred, characterized in that it contains at least one compound of the formula VI,

R ⁴ -A ¹ -COX-A ² -R ⁵ VI

wherein

R ⁴ and R ^{5 are} each alkyl with 1-15 C atoms, in which also one or two non-adjacent CH ₂ groups by -O-, -CO-, -O-CO-, -CO-O- and / or

-CH = CH- can be replaced,

X O or S,

and

A ¹ and A ² each represent 1,4-phenylene or trans-1,4-cyclohexylene, one of the groups A ¹ and A ² optionally also 4,4'-biphenylyl or trans, trans-4,4'-bicyclohexyl .

Also preferred are ferroelectric phases according to the invention containing at least one compound of the formula VII

R ¹ -Q ¹ -A- (Q ² ) qR ² VII

wherein

R ¹ and R ² each independently of one another are a straight-chain alkyl group having 1 to 15 C atoms, in which one or more non-adjacent CH ₂ groups are also replaced by -O-, -S-, -CO-, CHCH ₃ -O-, - CHCH ₃ -, -CH-halogen-, CHCN-,

-O-CO-, -O-COO-, -CO-O- and / or -CH = CH- can be replaced,

Q ¹ and Q ² each independently, - (A ° -Z °) _p -, where

1,4-cyclohexylene which is unsubstituted or substituted one or more times by halogen atoms, CH ₃ and / or nitrile groups, in which also one or two non-adjacent CH ₂ groups by -O- and / or -S- and / or a Grouping by can be replaced

(Cy), or unsubstituted or mono- or polysubstituted by halogen atoms, CH ₃ and / or nitrile groups, 1,4-phenylene, in which one or more CH groups can also be replaced by N, (Ph) means one the radicals A ° also 2, 6-naphthylene (Na) or tetrahydro-2,6-naphthylene (4H-Na), optionally substituted by halogen or CN, Zº, Z ¹ each independently of one another -CO-O-, -O- CO- and Z ² -CH ₂ O-, OCH ₂ -, -CH ₂ CH ₂ -, -CHCNCH ₂ -, -CH ₂ -CHCN- or a single bond, and

1, 2 or 3, or in the case A = tetra- or octahydrophenanthrene also means O, where in the case A =

means at least one group Z ° CHCNCH ₂ - or -CH ₂ CHCN- and / or in at least one of the groups

R ₁ and R ₂ at least one CH ₂ group is replaced by -CHCN-. The compounds of formula VII can have straight-chain or branched wing groups R ¹ and / or R ² . Compounds with branched wing groups can be used in the form of the racemate or as optically active compounds. Achiral base mixtures of compounds of the formula VII and, if appropriate, further achiral components can be doped with chiral compounds of the formula I or additionally with other chiral compounds in order to obtain chirally tilted smectic phases.

Particularly preferred smaller groups of compounds are those of the formulas VIII to VII18:

Another particularly preferred smaller group of compounds are those of the formulas VII19 to VII22: R ¹ -A ° -Cy- (CH ₂ ) _r -CHCN-C _s H _{2s + 1} VI119

R ¹ -A ° -A ° -Cy- (CH ₂ ) r -CHCN-C _s H _{2s + 1} VII20

R ¹ -A ° -A ° -CHCN-CH ₂ -Cy-R ² VI121

R ¹ -A ° -A ° -CH ₂ -CHCN-Cy-R ² VII22

wherein r represents 0, 1, 2 or 3 (r + s) is 1 to 14.

Compounds of the formula I which have no s _c phases are also suitable as components of smectic phases according to the invention.

The phases of the invention can also compounds of the formula

contain, wherein R ¹ and R ^{2 are} those given in formula VII

Have meaning.

The compounds of the formula I ', some of which are known and others are new, are prepared by methods known per se, such as those described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag Stuttgart) are produced.

If desired, the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formula I 'or I ". Esters or thioesters of the formula I 'or I "(where R ¹ and / or R ² = alkyl, in which one or two CH ₂ groups have been replaced by -O-CO and / or -CO-O groups, and / or Z ¹ and / or Z ² = -O-CO-, -CO-O-, -S-CO- or -CO-S- and / or m = 1) can be correspondingly esterified

Carboxylic acids (or their reactive derivatives) with

Alcohols, phenols, thiols or thiophenols (or their reactive derivatives) can be obtained.

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

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

Another advantageous method is the reaction of the corresponding carboxylic acids with the appropriate ones

Alcohols or thiols in the presence of dialkylcarbodiimides.

The esterification is advantageously carried out in the presence of an inert solvent. In particular, ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, amides such as DMF, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfanol are particularly suitable. Solvents which are immiscible with water can at the same time advantageously be used for azeotropically distilling off the water formed during the esterification become. Occasionally, an excess of an organic base, for example pyridine, quinoline or triethylamine, can also be used as a solvent for the esterification, the addition of catalytic amounts of 4-dimethylaminopyridine having a particularly favorable effect. 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 ° and + 250 °, preferably between -20 ° and + 80 °. At these temperatures, the esterification reactions are usually complete after 15 minutes to 48 hours.

In particular, the reaction conditions for the esterification largely depend on the nature of the starting materials used. For example, a free carboxylic acid is usually reacted with a free alcohol, phenol, thioalcohol or thiophenol in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulfuric acid. A preferred reaction mode is the reaction of an acid anhydride or in particular an acid chloride with an alcohol or thiol, preferably in a basic medium, the bases being in particular alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are important. Another preferred embodiment of the esterification consists in first converting the alcohol, the phenol, the thiol or the thiophenol into the sodium or potassium alcoholate, phenolate, thiolate or thiophenolate, for example by treatment with etha nolische sodium or potassium hydroxide solution, this isolated and reacted with an acid anhydride or in particular acid chloride.

Furthermore, acetylenic thioethers can be hydrated in the presence of mercury catalysts to give the corresponding thioesters of the formula I (m = 1) (for example L. Brandsma, H. Bos, JF Arens in Viehe, "Acetylenes", Marcel Dekker, Inc. New York , 1969).

Ethers and thioethers of the formula I 'or I "(in which R ¹ and / or R ^{2 are} an alkyl group, in which one or two

CH ₂ groups are replaced by O and / or S atoms, and / or where Z ¹ and / or Z ² = -OCH ₂ -, -CH ₂ O-, -SCH ₂ - or

-CH ₂ S- and / or where m = 0) can be obtained by etherification of corresponding alcohols, phenols, thioalcohols or thiophenols; wherein the sulfhydryl or hydroxy compound is first appropriately converted into a corresponding metal derivative, for example by treatment with NaH, NaNH ₂ , NaOH, KOH, K ₂ CO ₃ or Na ₂ CO _3, into the corresponding alkali metal alcoholate, phenolate, thiolate or thiopenolate becomes.

This can then be reacted with appropriate alkyl halide, sulfonate or dialkyl sulfonate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between 20 ° and 100 °.

Thioethers of the formula I 'or I "(in which R ¹ and / or R ²

-Alkyl means, in which one or more CH ₂ groups by

S atoms are replaced, and / or m = 0) can preferably be obtained by reacting compounds of the formula II (in which X

N ⁺ ₂ , Cl, Br or J means) can be obtained with thio alcoholates. Copper (I) 'alkyl mercaptides (produced, for example, by R. Adams, A. Ferretti, J. Am. Chem. Soc, 811 4927 (1959)) in organic, basic solvents, such as, for example, pyridine and quinoline, with compounds of the formula II implemented.

In addition, sodium mercaptides are best reacted with aryl iodides in polar aprotic solvents such as DMF, dimethyl sulfoxide or in liquid ammonia with simultaneous exposure.

The reaction of alkali metal mercaptides with aryldiazonium compounds is further preferred.

A further preferred possibility of representation of the thioethers of the formula I 'or I "is the addition of the mercaptans of the formula II (X = SH) to alkenes. The reaction conditions here have to be based on the type of the olefin. While in the case of olefins with activated double bonds, catalytic amounts increase Base are required (e.g. Brason, Org. React. 5, 79 (1949)), strong acids or radical formers are usually required for non-activated double bonds (e.g. Griesbaum, Angew. Chem., 82, 276 (1970)).

The thioalcohols and thiophenols frequently required as starting compounds can be obtained by reducing the sulfonyl halides with LiAlH ₄ , by reductive cleavage of the disulfides with zinc and dilute acid or by reacting Grignard compounds with elemental sulfur. Furthermore, the methods described for the preparation of sulfides are also suitable for the preparation of the mercaptans if sodium sulfide is used instead of alkyl mercaptides.

Corresponding acid amides can be dehydrated to produce nitriles of the formula I 'or I "(in which R ² denotes CN). The amides can be obtained, for example, from corresponding esters or acid halides by reaction with ammonia. Examples of suitable water-releasing agents are inorganic acid chlorides such as

SOC1 ₂ , PC1 ₅ , POC1 ₃ , SO ₂ C1 ₂ , COC1 ₂ , furthermore P ₂ O ₅ , P ₂ S ₅ , A1C1 ₃ (for example as a double compound with NaCl), cyanuric chloride, aromatic sulfonic acids and sulfonic acid halides. You can in the presence or absence of an inert solvent at temperatures between about 0 ° and

Work 150 °; come as solvents e.g. Bases such as pyridine or triethylamine, aromatic hydrocarbons such as benzene, toluene or xylene or amides such as DMF into consideration.

For the preparation of the nitriles mentioned above

Formula I 'or I ", corresponding acid halides, preferably the chlorides, can also be reacted with sulfamide, advantageously in an inert solvent such as tetramethyl sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °. After customary working up, the nitriles can be used directly isolate.

For the preparation of nitriles of the formula I 'or I "(wherein

R ^{2 is} CN and / or aryl and / or A ¹ and / or A ² is substituted by at least one CN group) can also be corresponding chlorine or bromine compounds

Formula I are reacted with a cyanide, advantageously with a metal cyanide such as NaCN, KCN or Cu ₂ (CN) ₂ , for example in the presence of pyridine in an inert solvent such as DMF or N-methylpyrrolidone at temperatures between 20 ° and 200 °.

For the preparation of laterally substituted fluorine or chlorine compounds of the formula I 'or I "(in which A ¹ and / or A ^{2 are} aromatics, R ¹ and R ^{2 are} the customary ones

Corresponding aniline derivatives with sodium nitrite and either with tetrafluoroboric acid (for introducing an F atom) or with copper (I) chloride (for introducing a Cl atom) can also have meanings

Diazonium salts are implemented, which are then thermally decomposed at temperatures of 100 ° -140 °.

The connection of an aromatic nucleus with a non-aromatic nucleus or two non-aromatic nuclei is preferably obtained by condensation of a lithium, (trialkoxy) titanium or halogen magnesium organyl with a ketone or an aldehyde or nitrile, if an aliphatic group Z should be.

The organometallic compounds are made, for example, by metal-halogen exchange (e.g. according to Org.

React. 6, 339-366 (1951)) between the corresponding halogen compound and an organolithium compound such as preferably n-butyllithium, tert-butyl lithium or lithium naphthalenide or by conversion with magnesium shavings. The (trialkoxy) titanium compounds are obtained by metal-metal exchange from the corresponding halogen magnesium or lithium compounds (e.g. M.T. Reetz, Top. Curr. Chem. 106., 1 (1982)).

The linking of two aromatic rings or an aliphatic group Z with an aromatic ring is preferably carried out by Friedel-Crafts alkylation or acylation in that the corresponding halogenver bonds with the corresponding aromatic compound under Lewis acid catalysis. Suitable Lewis acids are, for example, SnCl ₄ , ZnCl ₂ and especially A1C1 ₃ and TiCl ₄ .

Furthermore, the linking of two aromatic rings by the Ullmann reaction (eg Synthesis 1974, 9) between aryl iodides with copper iodide, but preferably between an aryl-copper compound and an aryl iodide, or by the Gomberg-Bachmann reaction between an aryl Carry out the diazonium salt and the corresponding aromatic compound (for example Org. React. 2, 224 (1944)).

In addition, 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 H atoms.

Possible reducible groups are preferably carbonyl groups, in particular keto groups, furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen atoms. Preferred starting materials for the reduction are compounds corresponding to formula I'or I ", but which instead of a cyclohexane ring is a cyclohexene ring or cyclohexanone ring and / or instead of a -CH ₂ CH ₂ group a -CH = CH group and / or in place a -CH ₂ group a -CO group and / or instead of an H atom a free or a functionally modified (eg in the form of its p-toluenesulfonate) OH group and / or instead of an -S group a - SO group or an -SO ₂ group included. The reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 0 ° and about 200 ° and pressures between about 1 and 200 bar in an inert solvent, for example 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 (for example PtO ₂ , PdO), on a support (for example Pd on carbon or aluminum oxide) or in finely divided form.

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

Sulfoxides and sulfones can preferably be reduced with complex hydrides. In addition, the thioethers of the formula I 'or I "can also be obtained from them by heating with elemental sulfur.

Reductions with complex hydrides are also possible. For example, arylsulfonyloxy groups can be removed reductively with LiAlH ₄ , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent. Double bonds can be hydrogenated with tributyltin hydride. Suitable solvents are preferably ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, amides such as dimethylformamide, hexamethylphosphoric triamide, hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, tetrachlorethylene, sulfoxides such as dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropanol and other organic solvents such as acetonitrile and nitromethane. Water or mixtures of these solvents with one another and / or with water are also suitable for the above reaction. The reaction temperatures are between -20 and + 100 °, preferably between 0 and 50 °. At these temperatures, the reactions are usually complete after 30 minutes to 24 hours.

All other components (compounds of the formulas IV-VII) of the phases according to the invention are either known or can be prepared analogously to known compounds in a manner known per se.

The phases according to the invention are produced in a conventional manner. As a rule, the components are dissolved in one another, expediently 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 types of liquid-crystal display elements which have hitherto become known.

The following examples are intended to illustrate the invention without limiting it. Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius. The values for the spontaneous Polarization (P _s ) ind in nC. cm and apply to room temperature. They also mean: K: crystal-solid state, Sm: smectic phase (the index indicates the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase. The number between two symbols indicates the transition temperature in degrees Celsius. "Customary work-up" means optionally adding water, extraction with methylene chloride, ether or toluene, separating the phases, drying the organic phase, evaporating the organic phase, purifying the residue by distillation and / or crystallization and / or chromatography.

example 1

4-alkylthiobiphenyl-4'-carboxylic acid alkyl ester

To a mixture of .233 g of 1-octylthio-4-bromobenzene (made from 4-bromothiophenol, 1-bromooctane and sodium methoxide in methanol) and 1.11 toluene / tetrahydrofuran (9: 1) is first 532 at -20 ° C ml of a 1.6 molar solution of n-butyllithium in hexane, then a mixture of 222 g of chlorotitanium triisopropoxide and 500 ml of toluene / tetrahydrofuran (9: 1) was added under a protective gas atmosphere. After 15 minutes, 144.3 g of ethyl 4-cyclohexanone carboxylate (prepared by partial hydrogenation of ethyl 4-hydroxybenzoate) are added dropwise at -20 ° C. The alcohol obtained after neutralization with hydrochloric acid and phase separation is heated to boiling for 2 hours in a mixture of 1 liter of ethanol and 120 ml of concentrated hydrochloric acid without purification. After isolation, the cyclohexene derivative which crystallized out at -25 ° C. is dissolved in 2.9 l of toluene and mixed with 337 g of 2,3-dichloro-5, 6-dicyan-p-benzochi-non. After heating for 2 hours and working up normally, ethyl 4-octylthiobiphenyl-4'-carboxylate is obtained. IR (KBr pellet): = 1718 (C = O), 2872 (S-CH ₂ ) cm ^-1

¹ H NMR (200 MHz, CDCl ₃ / TMS): δ = 0.86 (CH ₃ -C ₇ H ₁₄ -); 1.20-1.40 (CH ₃ -C ₅ H ₁₀ ); 1.39 (CO ₂ -CH ₂ CH ₃ ); 1.68 (S-CH ₂ -CH _2); 2.94 _(S-CH2); 4.39

(CO ₂ -CH ₂ ); 7.35-7.58 (SC ₆ H ₄ -); 7.58-8.12 (C ₆ H ₄ -CO ₂ ) ppm.

The following are represented in the same way:

4-Methylthiobiphenyl-4'-carboxylic acid ethyl ester 4-ethylthiobiphenyl-4'-carboxylic acid ethyl ester 4-propylthiobiphenyl-4'-carboxylic acid ethyl ester 4-butylthiobiphenyl-4'-carboxylic acid ethyl ester

Ethyl 4-pentylthiobiphenyl-4'-carboxylate 4-Hexylthiobiphenyl-4'-carboxylate 4-Heptylthiobiphenyl-4'-carboxylate 4-Nonylthiobiphenyl-4'-carboxylate 4-Decylthiobiphenyl-4'-carboxylate

4-Undecylthiobiphenyl-4'-carboxylic acid ethyl ester 4-Oct-3-enylthiobiphenyl-4'-carboxylic acid ethyl ester

Pentyl 4-pentylthiobiphenyl-4'-carboxylate 4-hexylthiobiphenyl-4'-carboxylate 4-heptylthiobiphenyl-4'-carboxylate 4-octylthiobiphenyl-4'-carboxylate pentyl 4-nonylthiobiphenyl-4'-carboxylate 4'-carboxylate

4-Pentylthiobiphenyl-4'-carboxylic acid octyl ester 4-Hexylthiobiphenyl-4'-carboxylic acid octyl ester 4-heptylthiobiphenyl-4'-carboxylic acid octyl ester 4-octylthiobiphenyl-4'-carboxylic acid octyl ester 4-nonylthiobiphenyl-4'-carboxylic acid octyl ester 4-decylthiobiphenyl-4'-carboxylic acid octyl ester

Example 2

4-alkylthiobiphenyl-4'-carboxylic acids

172.5 g of 4-octylthiobiphenyl-4'-carboxylic acid ethyl ester (shown in Example 1) are added to a mixture of 184 g of potassium hydroxide, 1.5 1 of ethanol and 0.84 1 of water; This mixture is heated to boiling for 2 hours and, after cooling, is concentrated with 0.28 l

Hydrochloric acid added. 4-Octylthiobiphenyl-4'-carboxylic acid is obtained after customary working up.

The following are represented in the same way:

4-methylthiobiphenyl-4'-carboxylic acid 4-ethylthiobiphenyl-4'-carboxylic acid

4-propylthiobiphenyl-4'-carboxylic acid

4-butylthiobiphenyl-4'-carboxylic acid

4-pentylthiobiphenyl-4'-carboxylic acid

4-hexylthiobiphenyl-4'-carboxylic acid 4-heptylthiobiphenyl-4'-carboxylic acid

4-nonylthiobiphenyl-4'-carboxylic acid

4-decylthiobiphenyl-4 .'-carboxylic acid

4-undecylthiobiphenyl-4'-carboxylic acid

4-oct-3-enylthiobiphenyl-4'-carboxylic acid

Example 3

4-alkylthiobiphenyl-4'-carboxylic acid aryl ester

A mixture of 23.1 g of 4-octylthiobiphenyl-4'-carboxylic acid chloride (prepared from that according to Example 2 carboxylic acid obtained with oxalyl chloride in toluene) and 46 ml of dichloromethane is converted into a mixture of 17.6 g of 4-hydroxybenzoic acid octyl ester (prepared from 4-hydroxybenzoic acid and octanol with p-toluenesulfonic acid), 5.6 g of pyridine, 0.5 g of 4-dimethylaminopyridine and 184 1 dichloromethane. After stirring for 10 hours at room temperature, the mixture is washed with dilute hydrochloric acid, saturated sodium bicarbonate solution and water. After the usual work-up, 4- (4-octylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester is obtained. K 104 SmC 125 SmA 162 I

The following are produced analogously:

4- (4-Pentylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester 4- (4-hexylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester 4- (4-heptylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester

4- (4-Oct-3-enylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester

4- (4-Nonylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester

4- (4-Decylthiobiphenyl-4'-carbonyloxy) benzoic acid octyl ester

4- (4-Pentylthiobiphenyl-4'-carbonyloxy) benzoic acid pentyl 4- (4-hexylthiobiphenyl-4'-carbonyloxy) benzoate

4- (4-Heptylthiobiphenyl-4'-carbonyloxy) benzoic acid pentyl ester

4- (4-Octylthiobiphenyl-4'-carbonyloxy) benzoic acid pentyl ester 4- (4-Nonylthiobiphenyl-4'-carbonyloxy) benzoic acid pentyl ester

4- (4-Decylthiobiphenyl-4'-carbonyloxy) benzoic acid pentyl ester

4- (4-Pentylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester

4- (4-Hexylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester

4- (4-Heptylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester

4- (4-Octylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester

4- (4-Nonylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester 4- (4-decylthiobiphenyl-4'-carbonyloxy) benzoic acid decyl ester

2- (4- (4-Pentylthiobiphenyl-4'-carbonyloxy) phenyl) -5-nonylpyrimidine

2- (4- (4-Hexylthiobiphenyl-4'-carbonyloxy) phenyl) -5-nonylpyrimidine

2- (4- (4-heptylthiobiphenyl-4'-carbonyloxy) phenyl) -5-nonylpyrimidine

2- (4- (4-octylthiobiphenyl-4'-carbonyloxy) phenyl) -5-nonylpyrimidine K 116 SmC 180 N 231 I.

2- (4- (4-Pentylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine

2- (4- (4-Hexylthiobiphenyl-4 * carbonyloxy) phenyl) -5-hexylpyrimidine gives 2- (4- (4-heptylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine

2- (4- (4-Octylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine 2- (4- (4-Oct-3-enylthiobiphenyl-4'-carbonyloxy) phenyl) • 5-hexylpyrimidine

2- (4- (4-Nonylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine gives 2- (4- (4-decylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine

2- (4- (4-Dodecylthiobiphenyl-4'-carbonyloxy) phenyl) -5-hexylpyrimidine

2- (4- (4-Pentylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Hexylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Heptylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine gives 2- (4- (4-octylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Nonylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Decylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Undecylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-dodecylthiobiphenyl-4'-carbonyloxy) phenyl) -5-ethylpyrimidine

2- (4- (4-Pentylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

2- (4- (4-Hexylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

2- (4- (4-heptylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

2- (4- (4-octylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

2- (4- (4-Nonylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine 2- (4- (4-decylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

2- (4- (4-dodecylthiobiphenyl-4'-carbonyloxy) phenyl) -5-octylpyrimidine

Example 4

4-alkylthiobiphenyl-4'-carboxylic acid ester

A mixture of 13.2 g of dicyclohexycarbodiimide and 13 ml is added to a mixture of 21.9 g of 4-octylthiobiphenyl-4'-carboxylic acid (prepared according to Example 2), 12.4 g of heptylphenol, 1 g of 4-dimethylaminopyridine and 150 ml of toluene Given toluene. After 4 hours of stirring at room temperature, the mixture is mixed with 0.2 g of oxalic acid and stirred for a further 30 minutes. After the usual work-up, 4- (4-octylthiobiphenyl-4'-carbonyloxy) -heptylbenzene is obtained.

K 93 Sm? (92) SmB 109 SmC 114 SmA 163 I

The following are produced analogously:

4- (4-Pentylthiobiphenyl-4'-carbonyloxy) heptylbenzene 4- (4-Hexylthiobiphenyl-4'-carbonyloxy) heptylbenzene 4- (4-heptylthiobiphenyl-4'-carbonyloxy) heptylbenzene

4- (4-Oct-3-enylthiobiphenyl-4'-carbonyloxy) heptylbenzene 4- (4-nonylthiobiphenyl-4'-carbonyloxy) heptylbenzene 4- (4-decylthiobiphenyl-4'-carbonyloxy) heptylbenzene 4- (4 -Dodecylthiobiphenyl-4'-carbonyloxy) -heptylbenzene

4- (4-pentylthiobiphenyl-4'-carbonyloxy) dodecylbenzene 4- (4-hexylthiobiphenyl-4'-carbonyloxy) dodecylbenzene 4- (4-heptylthiobiphenyl-4'-carbonyloxy) dodecylbenzene 4- (4-octylthiobiphenyl '-carbonyloxy) -dodecylbenzene 4- (4-nonylthiobiphenyl-4'-carbonyloxy) -dodecylbenzene 4- (4-decylthiobiphenyl-4'-carbonyloxy) -dodecylbenzene 4- (4-Pentylthiobiphenyl-4'-carbonyloxy) octylbenzene 4- (4-Hexylthiobiphenyl-4'-carbonyloxy) octylbenzene 4- (4-heptylthiobiphenyl-4'-carbonyloxy) octylbenzene 4- (4-octylthiobiphenyl-4 '-carbonyloxy) octylbenzene 4- (4-nonylthiobiphenyl-4'-carbonyloxy) octylbenzene 4- (4-decylthiobiphenyl-4'-carbonyloxy) octylbenzene

Analogously, the following optically active compounds are obtained in the esterification with (S) -lactic acid esters:

(S) -2- (4-Pentylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Hexylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Heptylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Octylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Nonylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester (S) -2- (4-decylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Undecylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Dodecylthiobiphenyl-4'-carbonyloxy) propionic acid ethyl ester

(S) -2- (4-Pentylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester

(S) -2- (4-Hexylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester (S) -2- (4-heptylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester

(S) -2- (4-Octylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester (S) -2- (4-Nonylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester

(S) -2- (4-Decylthiobiphenyl-4'-carbonyloxy) propionic acid octyl ester

(S) -2- (4-Pentylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-Hexylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-heptylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-Octylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-Nonylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester (S) -2- (4-decylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-Undecylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

(S) -2- (4-Dodecylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester

Example 5

4-alkylthiobiphenyl-4'-ols

A mixture of 64.4 g of 4-trimethylsiloxy-4'-bromobiphenyl (made from 4-hydroxy-4'-bromobiphenyl and trimethylchlorosilane in dichloromethane), 91.8 g of copper (I) octyl mercaptide (made analogously to R. Adams, A. Ferretti, J. Am. Chem. Soc. 81, 4927 (1959)) 200 ml of quinoline and 64 ml of pyridine are heated to 165 ° C. under a protective gas atmosphere for 3.5 hours. After cooling to 100 ° C., this mixture is poured onto a mixture of 1200 g of ice and 320 ml of concentrated hydrochloric acid. After extraction with Tert-butyl methyl ether, filtration, washing with concentrated ammonia solution and water are worked up as usual. 4-Octylthiobiphenyl-4'-ol is obtained. IR (KBr pellet): = 3423 (OH); 2872 (S-CH ₂₎ cm ^-1

¹ H NMR (200 MHz, CDCI ₃ / TMS): δ = 0.83 (CH ₃ -CH ₂ ); 1.18-1.46 (CgH ₁₀ ); 1.57 (S-CH ₂ -CH _2); 2.95 _(S-CH2); 6.80-7.45 (OC ₆ -H ₄ ); 7.46-7.51 (S-CgH4); 9.50 (OH) ppm.

The following are represented in the same way:

4-methylthiobiphenyl-4'-ol

4-ethylthiobiphenyl-4'-ol

4-propylthiobiphenyl-4'-ol

4-butylthiobiphenyl-4'-ol

4-pentylthiobiphenyϊ-4'-ol 4-hexylthiobiphenyl-4'-ol

4-heptylthiobiphenyl-4'-ol

4-oct-3-enylthiobiphenyl-4'-ol

4-nonylthiobiphenyl-4'-ol

4-decylthiobiphenyl-4'-ol 4-undecylthiobiphenyl-4'-ol

4-dodecylthiobiphenyl-4'-ol

Example 6

4-alkylthio-4'-alkyloxy-biphenyl

A mixture of 31.5 g of 4-octylthiobiphenyl-4'-ol (prepared according to Example 5) and 2 g of sodium ethanolate in 30 ml of ethanol is mixed with 25.2 g of octyl iodide and heated to boiling for 5 hours. After distilling off the alcohol, the reaction mixture is allowed to cool and poured onto 10 ml of 5% aqueous sodium hydroxide solution. After the usual work-up, 4-octylthio-4'-octyloxybiphenyl is obtained. The following are produced analogously

4-pentylthio-4'-octyloxybiphenyl 4-hexylthio-4'-octyloxybiphenyl 4-heptylthio-4'-octyloxybiphenyl 4-oct-3-enylthio-4'-octyloxybiphenyl 4-nonylthio-4'-octyloxybiphenyl 4-decylthio -octyloxybiphenyl 4-undecylthio-4'-octyloxybiphenyl

4-pentylthio-4'-pentyloxybiphenyl 4-hexylthio-4'-pentyloxybiphenyl

4-heptylthio-4'-pentyloxybiphenyl

4-octylthio-4'-pentyloxybiphenyl

4-nonylthio-4'-pentyloxybiphenyl

4-decylthio-4'-pentyloxybiphenyl 4-undecylthio-4'-pentyloxybiphenyl

4-dodecylthio-4'-pentyloxybiphenyl

4-pentylthio-4'-decyloxybiphenyl 4-hexylthio-4'-decyloxybiphenyl 4-heptylthio-4'-decyloxybiphenyl 4-octylthio-4'-decyloxybiphenyl 4-nonylthio-4'-decyloxybiphenyl 4-decylthio-4iphenyl And decylthio-4'-decyloxybiphenyl 4-dodecylthio-4'-decyloxybiphenyl

Example 7

4-alkylthio-4 '- (4-alkylthioarylcarbonyloxy) biphenyl

To a mixture of 7.5 g of dicyclohexycarbodiimide and 100 ml of tetrahydrofuran are 11.3 g of 4-octylthiobiphenyl-4'-ol (prepared according to Example 5) and 9.6 g of 4-octylthiobenzoic acid in succession at room temperature (made from 4-bromomagnesium octylthiobenzene and carbon dioxide). After stirring for 10 hours and separating off the solid constituents, working up is carried out as usual. 4- (4-Octylthiobenzoyloxy) -4'-octylthiobiphenyl is thus obtained. K 129 Sm? 150I

The following are produced analogously:

4- 4-octylthiobenzoyloxy) -4-pentylthiobiphenyl 4- 4-octylthiobenzoyloxy) -4-hexylthiobiphenyl 4- 4-octylthiobenzoyloxy) -4-heptylthiobiphenyl 4- 4-octylthiobenzoyloxy) -4-oct-3-enylthiobenzoyloxy) -4-nony1thiobiphenyl 4- 4-octylthiobenzoyloxy) -4-decylthiobiphenyl

4- 4-pentylthiobenzoyloxy) -4-pentylthiobiphenyl 4- 4-pentylthiobenzoyloxy) -4-hexylthiobiphenyl 4- 4-pentylthiobenzoyloxy) -4-heptylthiobiphenyl 4- 4-pentylthiobenzoyloxy) -4-octylthiobylthylobenzyli-4-pentylobenzyli-4-pentylthio 4- 4-pentylthiobenzoyloxy) -4-decylthiobiphenyl 4- 4-pentylthiobenzoyloxy) -4-undecylthiobiphenyl 4- 4-pentylthiobenzoyloxy) -4-dodecylthiobiphenyl

The following compounds are obtained analogously with 4-alkylthiobiphenyl-4'-carboxylic acid prepared according to Example 2:

4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-pentylthiobiphenyl

4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-hexylthiobiphenyl

4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-heptylthiobiphenyl 4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-octylthiobiphenyl 4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-nonylthiobiphenyl

4- (4-octylthiobiphenyl-4'-carbonyloxy) -4'-decylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-pentylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-hexylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-heptylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-octylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-nonylthiobiphenyl 4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-decylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-decylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-undecylthiobiphenyl

4- (4-pentylthiobiphenyl-4-carbonyloxy) -4'-dodecylthiobiphenyl

Example 8

4,4'-bis (alkylthio) biphenyl

A mixture of 114.7 g of copper (I) octyl mercaptide, 78.0 g of 4,4'-dibromobiphenyl, 250 ml of quinoline and 80 ml of pyridine gives 4,4-bis (octylthio) biphenyl analogously to Example 5 . K 114 I The following are produced analogously

4,4'-bis - ((methylthio) biphenyl

4,4'-bis - ((ethylthio) biphenyl

4,4'-bis - ((propylthio) biphenyl

4,4'-bis - ((butylthio) biphenyl

4,4'-bis - ((pentylthio) biphenyl

4,4'-bis - ((hexylthio) biphenyl

4,4'-bis - ((heptylthio) biphenyl

4,4'-bis - ((nonylthio) biphenyl

4,4'-bis - ((decylthio) biphenyl

4,4'-bis - ((undecylthio) biphenyl

4,4'-bis - ((dodecylthio) biphenyl

Example 9

(R) -2- (4-alkylthiobiphenyl-4'-oxy) propionic acid ester

To a mixture of 3.5 g of 4-octylthiobiphenyl-4'-ol

(prepared according to Example 5), 1.42 g of (S) ethyl lactate, 2.89 g of triphenylphosphine and 27.5 ml of tetrahydrofuran are added dropwise to 2.1 g of diethyl azodicarboxylate. The reaction mixture is heated to 50 ° C. for 2 hours and left to stand at room temperature for 10 hours. After customary working up, optically active (R) -2- (4-octylthiobiphenyl-4'-oxy) propionic acid ethyl ester is obtained. K 36.5 I

The following optically active connections are shown analogously:

(R) -2- (4-Pentylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-heptylthiobiphenyl-4'-oxy) propionic acid ethyl ester (R) -2- (4-Oct-3-enylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-Nonylthiobiphenyl-4'-oxy) propionic acid ethyl ester (R) -2- (4-decylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-Undecylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-Dodecylthiobiphenyl-4'-oxy) propionic acid ethyl ester

(R) -2- (4-Pentylthiobiphenyl-4'-oxy) propionic acid pentyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-oxy) propionic acid pentyl ester (R) -2- (4-heptylthiobiphenyl-4'-oxy) propionic acid pentyl ester

(R) -2- (4-Octylthiobiphenyl-4 '- oxy) propionic acid pentyl ester

(R) -2- (4-Nonylthiobiphenyl-4'-oxy) propionic acid pentyl ester

(R) -2- (4-Decylthiobiphenyl-4'-oxy) propionic acid pentyl ester

(R) -2- (4-Undecylthiobiphenyl-4'-oxy) propionic acid pentyl ester

(R) -2- (4-Pentylthiobiphenyl-4'-oxy) propionic acid octyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-oxy) propionic acid octyl ester (R) -2- (4-heptylthiobiphenyl-4'-oxy) propionic acid octyl ester

(R) -2- (4-Octylthiobiphenyl-4'-oxy) propionic acid octyl ester (R) -2- (4-Nonylthiobiphenyl-4'-oxy) propionic acid octyl ester

(R) -2- (4-Decylthiobiphenyl-4'-oxy) propionic acid octyl ester

(R) -2- (4-Pentylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-heptylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-Octylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-nonylthiobiphenyl-4'-oxy) propionic acid benzyl ester (R) -2- (4-decylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-Undecylthiobiphenyl-4'-oxy) propionic acid benzyl ester

(R) -2- (4-Dodecylthiobiphenyl-4'-oxy) propionic acid benzyl ester

Example 10

(S) -4-alkylthio-4 '- (2-chloroalkanoyloxy) biphenyl

A mixture is added to a mixture of 20.1 g of 4-octylthiobiphenyl-4'-ol (prepared according to Example 5), 8.2 g of (S) -2-chloro-3-methylbutyric acid, 1 g of 4-dimethylaminopyridine and 150 ml of toluene from 13.2 g of dicyclohexylcarbodiimide and 13 ml of toluene, the reaction mixture is given as in Example 4, treated and worked up in the usual way. Optically active (S) -4-octylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl is obtained. The following optically active connections are shown analogously:

(S) -4-pentylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl (S) -4-hexylthio-4' - (2-chloro-3-methylbutyryloxy) biphenyl

(S) -4-heptylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl

(S) -4-Oct-3-enylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl

(S) -4-nonylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl

(S) -4-decylthio-4 '- (2-chloro-3-methylbutyryloxy) biphenyl

(S) -4-pentylthio-4 '- (2-chloro (S) -4-methylpentanoyloxy) biphenyl

(S) -4-Hexylthio-4 '- (2-chloro (S) -4-methylpentanoyloxy) biphenyl

(S) -4-heptylthio-4 '- (2-chloro (S) -4-methylpentanoyloxy) biphenyl

(S) -4-octylthio-4 '- (2-chloro (S) -4-methylpentanoyloxy) biphenyl

(S) -4-nonylthio-4 '- (2-chloro (S) -4-methylpentanoyloxy) biphenyl (S) -4-decylthio-4' - (2-chloro (S) -4-methylpentanoyloxy) -biphenyl

(S) -4-pentylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl

(S) -4-Hexylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl

(S) -4-heptylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl (S) -4-octylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl

(S) -4-nonylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl (S) -4-decylthio-4' - (2-chloro-3-methylpentanoyloxy) biphenyl

(S) -4-Undecylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl

(S) -4-dodecylthio-4 '- (2-chloro-3-methylpentanoyloxy) biphenyl

Example 11

4-alkylbiphenyl-4'-thiol

3.3 g of finely powdered elemental sulfur are added to a mixture of 4-bromagnesium-4'-octylbiphenyl (prepared from 36.1 g of 4-octyl-4'-bromobiphenyl and 2.6 g of magnesium) and 150 ml of tetrahydrofuran. After stirring for 30 minutes at 65 ° C., lithium aluminum hydride is added after cooling to complete decolorization, and 4-octylbiphenyl-4'-thiol is obtained after customary working up.

The following are represented in the same way:

4-methylbiphenyl-4'-thiol

4-ethylbiphenyl-4'-thiol

4-propylbiphenyl-4'-thiol 4-butylbiphenyl-4'-thiol

4-pentylbiphenyl-4'-thiol

4-hexylbiphenyl-4'-thiol

4-heptylbiphenyl-4'-thiol

4-oct-3-enylbiphenyl-4'-thiol 4-nonylbiphenyl-4'-thiol 4-decylbiphenyl-4'-thiol 4-undecylbiphenyl-4'-thiol 4-dodecylbiphenyl-4'-thiol

If 4-alkoxy-4'-bromobiphenyl is used as the starting material, the following are obtained analogously:

4-ethyloxybiphenyl-4'-thiol

4-propyloxybiphenyl-4'-thiol

4-butyloxybiphenyl-4'-thiol

4-pentyloxybiphenyl-4'-thiol 4-hexyloxybiphenyl-4'-thiol

4-heptyloxybiphenyl-4'-thiol

4-octyloxybiphenyl-4'-thiol

4-nonyloxybiphenyl-4'-thiol

4-decyloxybiphenyl-4'-thiol 4-undecyloxybiphenyl-4'-thiol

4-dodecyloxybiphenyl-4'-thiol

Example 12

4-alkylthiobiphenyl-4'-thiols

Hydrogen sulfide is passed into an aqueous solution of 4-octylthiobiphenyl-4'-dia-zonium chloride, prepared from 4-bromo-4'-nitrobiphenyl by reaction with copper (I) octyl mercaptide (analogously to Example 5), reduction and subsequent diazotization and heated to 60 ° C. After the usual work-up, 4-octyltiobiphenyl-4'-thiol is obtained.

The following are produced analogously:

4-ethylthiobiphenyl-4'-thiol 4-propylthiobiphenyl-4'-thiol 4-butylthiobiphenyl-4'-thiol 4-pentylthiobiphenyl-4'-thiol 4-hexylthiobiphenyl-4'-thiol 4-heptylthiobiphenyl-4'-thiol 4-nonylthiobiphenyl-4'-thiol 4-decylthiobiphenyl-4'-thiol 4-undecylthiobiphenyl-4'-thi Dodecylthiobiphenyl-4'-thiol

Example 13

4-alkylthio-4'-alkylthiobiphenyl

From 33.1 g of 4-octylthiobiphenyl-4'-thiol (prepared according to Example 12) and 21.2 g of n-hexyl iodide, 4-hexylthio-4'-octylthiobiphenyl is obtained according to Example 6.

The following are produced analogously:

4-pentylthio-4'-octylthiobiphenyl 4-heptylthio-4'-octylthiobiphenyl 4-nonylthio-4'-octylthiobiphenyl 4-decylthio-4'-octylthiobiphenyl 4-undecylthio-4'-octylthiobiphenyl 4-dodecyl

4-pentylthio-4'-hexylthiobiphenyl

4-heptylthio-4'-hexylthiobiphenyl

4-nonylthio-4'-hexylthiobiphenyl

4-decylthio-4'-hexylthiobiphenyl

4-undecylthio-4'-hexylthiobiphenyl 4-dodecylthio-4'-hexylthiobiphenyl

4-pentylthio-4'-ethylthiobiphenyl 4-hexylthio-4'-ethylthiobiphenyl 4-heptylthio-4'-ethylthiobiphenyl 4-octylthio-4'-ethylthiobiphenyl 4-nonylthio-4'-ethylthiobiphenyl 4-decylthio-4'-ethylthiobiphenyl 4-undecylthio-4'-ethylthiobiphenyl 4-dodecylthio-4'-ethylthiobiphenyl

With 4-alkylbenzyl halides as alkylating agents, the following is obtained analogously:

4-pentylthio-4 '- (4-ethylbenzylthio) biphenyl 4-hexylthio-4' - (4-ethylbenzylthio) biphenyl 4-heptylthio-4 '- (4-ethylbenzylthio) biphenyl 4-octylthio-4' - ( 4-ethylbenzylthio) biphenyl 4-nonylthio-4 '- (4-ethylbenzylthio) biphenyl 4-decylthio-4' - (4-ethylbenzylthio) biphenyl 4-undecylthio-4 '- (4-ethylbenzylthio) biphenyl 4- Dodecylthio-4 '- (4-ethylbenzylthio) biphenyl

4-pentylthio-4 '- (4-butyloxybenzylthio) biphenyl 4-hexylthio-4' - (4-butyloxybenzylthio) biphenyl 4-heptylthio-4 '- (4-butyloxybenzylthio) biphenyl 4-octylthio-4' - ( 4-butyloxybenzylthio) biphenyl 4-nonylthio-4 '- (4-butyloxybenzylthio) biphenyl 4-decylthio-4' - (4-butyloxybenzylthio) biphenyl

4-pentylthio-4 '- (4-octylbenzylthio) biphenyl 4-hexylthio-4' - (4-octylbenzylthio) biphenyl 4-heptylthio-4 '- (4-octylbenzylthio) biphenyl 4-octylthio-4' - ( 4-octylbenzylthio) biphenyl 4-nonylthio-4 '- (4-octylbenzylthio) biphenyl 4-decylthio-4' - (4-octylbenzylthio) biphenyl

With the 4-alkylbiphenyl-4'-thiols as starting products, the following compounds are obtained:

4-pentylthio-4'-octylbiphenyl 4-hexylthio-4'-octylbiphenyl 4-heptylthio-4'-octylbiphenyl 4-octylthio-4'-octylbiphenyl 4-nonylthio-4'-octylbiphenyl 4-decylthio-4'-octylbiphenyl

4-pentylthio-4'-pentylbiphenyl 4-hexylthio-4'-pentylbiphenyl 4-heptylthio-4'-pentylbiphenyl 4-octylthio-4'-pentylbiphenyl 4-nonylthio-4'-pentylbiphenyl 4-decylentiobiphenyl

4-undecylthio-4'-pentylbiphenyl 4-dodecylthio-4'-pentylbiphenyl

Example 14

(R) -2- (4-alkylthiobiphenyl-4'-thio) propionic acid ester

3.7 g of 4-octylthiobiphenyl-4'-thiol, 1.42 g of (S) -ethyl lactate are obtained using the Mitsunobu reagent (2.1 g of diethyl azodicarboxylate, 2.89 g of triphenylphosphine) analogously to Example 9 ( R) -2- (4-Octylthiobiphenyl-4'-thio) propionic acid ethyl ester.

The following optically active connections are shown analogously:

(R) -2- (4-Pentylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Heptylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-O'ct-3-enylthiobiphenyl-4'-thio) propionic acid ethyl ester (R) -2- (4-Nonylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-decylthiobiphenyl-4'-thio) propionic acid ethyl ester (R) -2- (4-dodecylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Undecylthiobiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Pentylthiobiphenyl-4'-thio) propionic acid octyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-thio) propionic acid octyl ester

(R) -2- (4-Heptylthiobiphenyl-4'-thio) propionic acid octyl ester (R) -2- (4-octylthiobiphenyl-4'-thio) propionic acid octyl ester

(R) -2- (4-Nonylthiobiphenyl-4'-thio) propionic acid octyl ester

(R) -2- (4-Decylthiobiphenyl-4'-thio) propionic acid octyl ester

(R) -2- (4-Pentylthiobiphenyl-4'-thio) propionic acid benzyl ester

(R) -2- (4-Hexylthiobiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-heptylthiobiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-octylthiobiphenyl-4'- benzio thio) propionate

(R) -2- (4-Nonylthiobiphenyl-4'-thio) propionic acid benzyl ester

(R) -2- (4-Decylthiobiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-Undecylthiobiphenyl-4'-thio) propionic acid benzyl ester

(R) -2- (4-Dodecylthiobiphenyl-4'-thio) propionic acid benzyl ester

The following optically active compounds are obtained analogously with the 4-alkyloxybiphenyl-4'-thiol:

(R) -2- (4-Pentyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Hexyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Heptyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-octyloxybiphenyl-4'-thio) propionic acid ethyl ester (R) -2- (4-nonyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Decyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Undecyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-Dodecyloxybiphenyl-4'-thio) propionic acid ethyl ester

(R) -2- (4-pentyloxybenenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-hexyloxybiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4th -Heptyloxybiphenyl-4'-thio) -propionic acid benzyl ester (R) -2- (4-octyloxybiphenyl-4'-thio) -propionic acid-benzyl ester

(R) -2- (4-Nonyloxybiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-Decyloxybiphenyl-4'-thio) propionic acid benzyl ester

(R) -2- (4-undecyloxybiphenyl-4'-thio) propionic acid benzyl ester (R) -2- (4-dodecyloxybiphenyl-4'-thio) propionic acid benzyl ester

Example 15

4-alkyl-4'-alkanoylthiobiphenyl

From 17.9 g of 4-octylbiphenyl-4'-thiol (prepared according to Example 11) and 9.2 g of octanoic acid, 104-octyl-4'-octanoylthiobiphenyl is obtained according to Example.

The following are also shown:

4-pentyl-4'-octanoylthiobiphenyl 4-hexyl-4'-octanoylthiobiphenyl 4-heptyl-4'-octanoylthiobiphenyl 4-nonyl-4'-octanoylthiobiphenyl 4-decyl-4'-octanoylthiobiphenyl

4-pentyloxy-4'-octanoylthiobiphenyl 4-hexyloxy-4'-octanoylthiobiphenyl 4.-heptyloxy-4'-octanoylthiobiphenyl 4-octyloxy-4'-octanoylthiobiphenyl 4-nonyloxy-4'-octanoylthiobiphenyl 4

4-pentylthio-4'-octanoylthiobiphenyl 4-hexylthio-4'-octanoylthiobiphenyl 4-heptylthio-4'-octanoylthiobiphenyl 4-octylthio-4'-octanoylthiobiphenyl 4-nonylthio-4'-octanoyipthyl 4-heptyloylthiobiphenyl Example 16

(S) -2-alkylthio-5- (4- (2-chloroalkanoyloxy) phenyl) pyrimidine

From 20.2 g of 2-octylthio-5- (4-hydroxyphenyl) pyrimidine (prepared by the condensation of octylthiuronium bromide and 4- (2- (1,1,3,3-tetramethoxy) propyl) phenol) and 8.2 g of (S) -2-chloro-3-methylbutyric acid are obtained according to Example 10 optically active (S) -2-octylthio-5- (4- (2-chloro-3-methylbutyryloxy) phenyl) pyrimidine.

The following are produced analogously:

(S) -2-pentylthio-5- (4- (2-chloro-3-methylbutyryloxy) phenyl) pyrimidine

(S) -2-hexylthio-5- (4- (2-chloro-3-methylbutyryloxy) phenyl) pyrimidine (S) -2-heptylthio-5- (4- (2-chloro-3-methylbutyryloxy) - phenyl) pyrimidine

(S) -2-nonylthio-5- (4- (2-chloro-3-methylbutyryloxy) phenyl) pyrimidine

(S) -2-decylthio-5- (4- (2-chloro-3-methylbutyryloxy) phenyl) pyrimidine

(S) -2-pentylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl) pyrimidine

(S) -2-hexylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl) pyrimidine (S) -2-heptylthio-5- (4- (2-chloro-4-methylpentanoyloxy) - phenyl) pyrimidine

(S) -2-octylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl) pyrimidine (S) -2-nonylthio-5- (4- (2-chloro-4-methylpentanoyloxy) - phenyl) pyrimidine (S) -2-decylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl) pyrimidine

(S) -2-undecylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl) pyrimidine (S) -2-dodecylthio-5- (4- (2-chloro-4-methylpentanoyloxy) phenyl ) pyrimidine

The following optically active propionic acid esters are obtained analogously by reacting 4- (2-alkylthio- (S) -pyrimidin-5-yl) -benzoic acid with (S) -lactic acid esters:

(S) 2- (4- (2-Pentylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Hexylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Heptylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Octylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Nonylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester (S) -2- (4- (2-decylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Undecylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Dodecylthiopyrimidin-5-yl) benzoyloxy) propionic acid ethyl ester

(S) -2- (4- (2-Pentylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester

(S) -2- (4- (2-Hexylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester (S) -2- (4- (2-heptylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester

(S) -2- (4- (2-Octylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester (S) -2- (4- (2-Nonylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester

(S) -2- (4- (2-decylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester (S) -2- (4- (2-dodecylthiopyrimidin-5-yl) benzoyloxy) propionic acid benzyl ester

Example 17

(R) -2- (4- (2-alkylthiopyrimidin-5-yl) phenyloxy) propionic acid ester

With the Mitsunobu reagent, 3.5 g of 2-octylthio-5- (4-hydroxyphenyl) pyrimidine and 1.42 g of (S) ethyl lactate are used to obtain (2.89 g triphenylphosphine and 2.1 g diethylazodicar boxylate) according to Example 9 optically active (R) -2- (4- (2-octylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester.

The following are represented in the same way:

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester (R) -2- (4- (2-heptylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester

(R) -2- (4- (2-Oct-3-enylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenyloxy) ethyl propionate

(R) -2- (4- (2-Decylthiopyrimidin-5-yl) phenyloxy) ethyl propionate

(R) -2- (4- (2-Undecylthiopyrimidin-5-yl) phenyloxy) ethyl propionate (R) -2- (4- (2-dodecylthiopyrimidin-5-yl) phenyloxy) ethyl propionate (R) -2- (4- (2-Pentylthiopyrimidin-5-yl) phenyloxy) propionic acid octyl ester

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenyloxy) propionic acid octyl ester (R) -2- (4- (2-heptylthiopyrimidin-5-yl) phenyloxy) propionic acid octyl ester

(R) -2- (4- (2-Octylthiopyrimidin-5-yl) phenyloxy) propionic acid octyl ester

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenyloxy) propionic acid octyl ester

(R) -2- (4- (2-Decylthiopyrimidin-5-yl) phenyloxy) propionic acid ethyl ester

(R) -2- (4- (2-pentylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester (R) -2- (4- (2-hexylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

(R) -2- (4- (2-Heptylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

(R) -2- (4- (2-Octylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

(R) -2- (4- (2-decylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester (R) -2- (4- (2-undecylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

(R) -2- (4- (2-Dodecylthiopyrimidin-5-yl) phenyloxy) propionic acid benzyl ester

With 2-alkylthio-5- (4-sulfhydrylphenyl) pyrimidine as the starting material, the following is obtained analogously:

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester (R) -2- (4- (2-Heptylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Octyithiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester (R) -2- (4- (2-nonylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Decylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Undecylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Dodecylthiopyrimidin-5-yl) phenylthio) propionic acid ethyl ester

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) -phenylthio) -propionic acid octyl ester (R) -2- (4- (2-hexylthiopyrimidin-5-yl) -phenylthio) -propionic acid octyl ester

(R) -2- (4- (2-Heptylthiopyrimidin-5-yl) phenylthio) propionic acid octyl ester

(R) -2- (4- (2-Octylthiopyrimidin-5-yl) phenylthio) propionic acid octyl ester

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenylthio) propionic acid octyl ester

(R) -2- (4- (2-Decylthiopyrimidin-5-yl) phenylthio) propionic acid octyl ester

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) phenylthio) propionic acid benzyl ester

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenylthio) propionic acid benzyl ester

(R) -2- (4- (2-heptylthiopyrimidin-5-yl) phenylthio) benzyl propionate

(R) -2- (4- (2-Octylthiopyrimidin-5-yl) phenylthio) benzyl propionate

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenylthio) benzyl propionate (R) -2- (4- (2-Decylthiopyrimidin-5-yl) phenylthio) propionic acid benzyl ester

(R) -2- (4- (2-Dodecylthiopyrimidin-5-yl) phenylthio) propionic acid benzyl ester

Example 18

(R) -2- (4-alkylthiobiphenyl-4'-carbonyloxy) propionitrile

A mixture of 12.6 g of (R) -2- (4-octylthiobiphenyl-4'-carbonyloxy) propionic acid benzyl ester (prepared according to Example 4), 150 ml of ethyl acetate and 200 mg of Pd / C (5%) is at normal pressure and room temperature hydrated. The free carboxylic acid thus obtained is converted into the corresponding acid chloride with oxalyl chloride, which is dissolved in 20. ml of diglyme, mixed with 25 ml of an aqueous solution of ammonia (d = 0.88) and stirred for 2 hours at room temperature. The acid amide obtained after the usual work-up is used without purification. A mixture of 0.6 g of thionyl chloride, 10 ml of DMF is added to a mixture of 2.5 g of the acid amide thus prepared and 30 ml of DMF. After stirring for 2 hours at room temperature and customary working up, optically active (R) -2- (4-octylthiobiphenyl-4'-carbonyloxy) propionitrile is obtained.

The following optically active connections are made analogously:

(R) -2- (4-pentylthiobiphenyl-4'-carbonyloxy) propionitrile

(R) -2- (4-hexylthiobiphenyl-4'-carbonyloxy) propionitrile (R) -2- (4-heptylthiobiphenyl-4'-carbonyloxy) propionitrile (R) -2- (4-Oct-3-enylthiobiphenyl-4'-carbonyloxy) propionitrile

(R) -2- (4-nonylthiobiphenyl-4'-carbonyloxy) propionitrile (R) -2- (4-decylthiobiphenyl-4'-carbonyloxy) propionitrile

(R) -2- (4-Undecylthiobiphenyl-4'-carbonyloxy) propionitrile

(R) -2- (4-dodecylthiobiphenyl-4'-carbonyloxy) propionitrile

Analogously, the following optically active compounds are obtained with (R) -2- (4-alkylthiobiphenyl-4'-oxy) propionic acid benzyl esters (prepared according to Example 9):

(R) -2- (4-pentylthiophenyl-4'-oxy) propionitrile (R) -2- (4-hexylthiophenyl-4'-oxy) propionitrile (R) -2- (4-heptylthiophenyl-4'- oxy) propionitrile (R) -2- (4-octylthiophenyl-4'-oxy) propionitrile (R) -2- (4-nonylthiophenyl-4'-oxy) propionitrile (R) -2- (4-decylthiophenyl -4'-oxy) propionitrile (R) -2- (4-undecylthiophenyl-4'-oxy) propionitrile (R) -2- (4-dodecylthiophenyl-4'-oxy) propionitrile

Analogously, with (R) -2- (4-alkyloxybiphenyl-4'-thio) propionic acid benzyl esters (prepared according to Example 14) the following optically active compounds are obtained as starting products:

(R) -2- (4-pentyloxybiphenyl-4'-thio) propionitrile (R) -2- (4-hexyloxybiphenyl-4'-thio) propionitrile (R) -2- (4-heptyloxybiphenyl-4'- thio) propionitrile (R) -2- (4-octyloxybiphenyl-4'-thio) propionitrile (R) -2- (4-nonyloxybiphenyl-4'-thio) propionitrile (R) -2- (4-decyloxybiphenyl -4'-thio) propionitrile

(R) -2- (4-dodecyloxybiphenyl-4'-thio) propionitrile (R) -2- (4-oct-3-enyloxybiphenyl-4'-thio) propionitrile The following optically active (R) propionitriles are obtained analogously with the (R) -propionic acid benzyl esters prepared in Example 17 as starting compounds:

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-heptylthiopyrimidin-5-yl) phenyloxy) propionitrile (R) -2- (4- (2-octylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-decylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-Undecyl'thiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-dodecylthiopyrimidin-5-yl) phenyloxy) propionitrile

(R) -2- (4- (2-pentylthiopyrimidin-5-yl) phenylthio) propionitrile

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) phenylthio) propionitrile (R) -2- (4- (2-heptylthiopyrimidin-5-yl) phenylthio) propionitrile

(R) -2- (4- (2-Octylthiopyrimidin-5-yl) phenylthio) propionitrile

(R) -2- (4- (2-nonylthiopyrimidin-5-yl) phenylthio) propionitrile (R) -2- (4- (2-decylthiopyrimidin-5-yl) phenylthio) propionitrile (R) -2- (4- (2-Undecylthiopyrimidin-5-yl) phenylthio) propionitrile

(R) -2- (4- (2-dodecylthiopyrimidin-5-yl) phenylthio) propionitrile

The following optically active (R) -2-benzoyloxypropionitriles are obtained analogously with the (R) -2-benzoyloxypropionic acid benzyl esters prepared in Example 16 as starting compounds:

(R) -2- (4- (2-Pentylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-Hexylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-heptylthiopyrimidin-5-yl) benzoyloxy) propionitrile (R) -2- (4- (2-octylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-Nonylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-decylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-Undecylthiopyrimidin-5-yl) benzoyloxy) propionitrile

(R) -2- (4- (2-dodecylthiopyrimidin-5-yl) benzoyloxy) propionitrile

Mixture example A

5% 2-p-hexyloxyphenyl-5-heptylpyrimidine

4% 2-p-heptyloxyphenyl-5-heptylpyrimidine

5% 2-p-octyloxyphenyl-5-octylpyrimidine 8% 2-p-nonyloxyphenyl-5-octylpyrimidine 10% 2-p-decyloxyphenyl-5-octylpyrimidine

8% 2-p-hexyloxyphenyl-5-nonylpyrimidine

25% 2-p-nonyloxyphenyl-5-nonylpyrimidine 12% 2-p-octyloxyphenyl-5-heptylphenylthiazole 15% (S) - (4- (5-heptylpyrimidin-2-yl) phenyl) - (2-chloro-3-methyl (butyrate) 8% 4-octylthio- 4 '- (4- (5-nonylpyrimidin-2-yl) benzoyloxy) biphenyl

SmC 67 SmA 82 Ch 94 I, P _s = 14

Mixing example B

4% 2-p-hexyloxyphenyl-5-heptylpyrimidine

5% 2-p-heptyloxyphenyl-5-heptylpyrimidine 5% 2-p-octyloxyphenyl-5-heptylpyrimidine

5% 2-p-nonyloxyphenyl-5-heptylpyrimidine

7% 2-p-hexyloxypheny1-5-nonylpyrimidine

5% 2-p-heptyloxyphenyl-5-nonylpyrimidine

4% 2-p-octyloxyphenyl-5-nonylpyrimidine 25% 2-p-nonyloxyphenyl-5-nonylpyrimidine

12% (S) - (4- (5-heptylpyridin-2-yl) phenyl) - (2-chloro-3-methylbutyrate)

10% 4-octylthio-4 '- (4-heptylbenzoyloxy) biphenyl

8% 4-octylthio-4 '- (4-nonylbenzoyloxy) biphenyl 10% 4-octylthio-4' - (4-octyloxybenzoyloxy) biphenyl

SmC 62 SmA 69 Ch 85 I, P = 12

Mixture example C

5% 2-p-hexyloxyphenyl-5-heptylpyrimidine

5% 2-p-heptyloxyphenyl-5-heptylpyrimidine 4% 2-p-octyloxyphenyl-5-heptylpyrimidine

4% 2-p-nonyloxyphenyl-5-heptylpyrimidine

8% 2-p-octyloxyphenyl-5-octylpyrimidine 10% 2-p-nonyloxyphenyl-5-octylpyrimidine 5% 2-p-nonyloxyphenyl-5-nonylpyrimidine 2% (S) - (4- (5-heptylpyrimidin-2-yl) phenyl) - (2-chloro-3-methylbutyrate)

6% 4-heptylthio-4'-octyloxybiphenyl

6% 4-nonylthio-4'-octyloxybiphenyl

15% 4-octylthio-4 '- (4-octyloxybenzoyloxy) biphenyl

SmC 55 SmA 65 Ch 82 I

Claims

Claims

1. Use of compounds of the formula I,

R ¹ - (CO) _m -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ²

wherein

R ¹ and R ^{2 are} each independently an unsubstituted or substituted with -CN or with at least one halogen

Alkyl or alkenyl radical with up to

18 carbon atoms, in which one or more CH ₂ groups can be replaced by a radical selected from the group -O-,

-S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- and

-C≡C-, where 2 heteroatoms are not adjacent, R ² also H, F, Cl, CN, Br or CF ₃ ,

Aryl unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups 1,4-phenylene, pyridine -2,5-diyl, pyrimidine-2,5-diyl , Pyrazine-2,5-diyl or pyridazine-2,5-diyl, Z ¹ and Z ² each -CO-O-, -CO-S-, -O-CO-, -S-CO-,

-CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, or a single bond,

A ¹ and A ² each independently

a) a 1,4-phenylene radical, in which one or two CH groups can be replaced by N.

b) a 1,4-cyclohexylene radical, in which one or two non-adjacent CH ₂ groups can be replaced by -O- and / or -S-.

c) a 1,4-cyclohexenylene, a 1,4-bicyclo [2,2,2] octylene, a naphthalene 2,6-diyl, a decahydronaphthalene 2,6-diyl, a 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl or a piperidine-1,4-diyl radical,

where the radicals a) and b) can be substituted one or more times by halogen atoms, cyano and / or methyl groups,

m 0 or 1, and

n 0, 1 or 2

means, where in the case n = 2 the A ¹ or Z ² radicals can each be the same or different, with the proviso that for optically active

Compounds of formula I wherein n is O, m = O and A unsubstituted or once or twice

F, Cl, CH ₃ and / or CN substituted 1,4 phenylene or 1,4 cyclohexylene, in which one or two non-adjacent CH ₂ groups can also be replaced by -O- and / or -S-, means as components of ferroelectric liquid-crystalline phases.

2. Compounds of the formula I ',

R ¹ - (CO) _m -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² I '

wherein

R ¹ and R ^{2 are} each independently an unsubstituted or substituted with -CN or with at least one halogen

Alkyl or alkenyl radical with up to

18 carbon atoms, in which one or more

CH ₂ groups can be replaced by a radical selected from the group -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- and

-C = C-, where 2 heteroatoms are not adjacent, R ² also F, Cl, Br, OH, SH or CN,

R ¹ also H,

Aryl-1,4-phenylene which is unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups,

A ¹ and A ² 1,4-phenylene which is unsubstituted or substituted by F, Cl, CH ₃ and / or CN,

Z ^{1 represents} a single bond, and

m and n have the meaning given, with the proviso that if n = O

R is an alkyloxy, alkylthio, alkoxycarbonyl,

Alkanoyloxy or perfluoroalkyl group each having 1-12 C atoms, in which one or more CH ₂ or CF ₂ groups are also selected by a group from the group -O-, -S-, -CO-, -O-CO- , -S-CO-, -O-COO-, -CO-O-, -CO-S-, -CH = CH-, C (CH ₃ ) = CH-, -CH = C (CH ₃ ) -, -CH-halogen and CH-CN- can be replaced, two heteroatoms not being directly linked, F, Cl, Br, OH, SH or CN,

and / or one of the rings

Aryl or A ^{2 means} F, Cl, CH ₃ and / or CN substituted 1,4 phenylene.

3. Compounds of the formula I "

R ¹ - (CO) _m -S-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² I "

wherein R ¹ , R ² , aryl, A ¹ , A ² , Z ¹ , Z ² m and n di.e.

Formula I have the meaning given, with the provisos that

a) n is 2 if R is branched and aryl is unsubstituted or substituted 1,4-phenylene, and

b) aryl means pyridine-2, 5-diyl or pyrimidine-2, 5-diyl or the group linked to Z is 1,4-phenylene, in which one or two CH groups are replaced by N.

4. Process for the preparation of the compounds of

Formula I 'and I ", characterized in that p-lithium, p-halogen magnesium or p-trialkoxytitanium (alkylthio) aryl compounds are reacted with aldehydes, ketones or nitriles, or that compounds of the formula II,

X-aryl-Z ¹ - (A ¹ -Z ² ) _n -A ² -R ² II

wherein

XN represents ₂ ⁺ , Cl, Br or J, and

Aryl, A ¹ , A ² , Z ¹ , Z ² , R ² and n have the meaning given, with alkyl or alkanoyl thiolate compounds of the formula III,

R ¹ - (CO) _m mSM III

in which R ¹ and m have the meaning given, and M denotes a monovalent metal, or in that compound of the formula II,

wherein

X SH means and

Aryl, A ¹ , A ² , Z ¹ , Z ² , R ² and n have the meaning given, reacted with alkenes or ketones,

or that a compound which otherwise corresponds to the formula I 'or I "but contains one or more reducible groups and / or CC bonds instead of H atoms and / or a sulfoxide group instead of a mercapto group, with a reducing agents treated or that for the preparation of esters or thioesters of the formula I 'or I "(in which m = 1 and / or R ¹ or R ^{2 contains} a carboxyl or thiocarboxyl group and / or Z ¹ or Z ² -CO-O-, - CO-S-, -O-CO- or -S-CO- mean a corresponding carboxylic acid or one of its reactive derivatives with a corresponding alcohol, thiol or its reactive

Implements derivatives,

or that for the preparation of ethers or thioethers of the formula I 'or I "(in which R ¹ or R ^{2 is} a

Alkoxy, oxaalkyl or thioalkyl group means and / or m = O and / or Z ¹ or Z ² -OCH ₂ -, -CH ₂ O-,

-SCH ₂ - or -CH ₂ S- mean a corresponding one

Hydroxy or sulfhydryl group etherified.

5. Ferroelectric liquid-crystalline phase with at least two liquid-crystalline components, characterized in that it contains at least one compound of the formula I.

6. Electro-optical display element, characterized in that it contains a phase as claimed in claim 5 as a dielectric.