JPH024768A - Trane derivative - Google Patents

Abstract

NEW MATERIAL: A compound of the formula [wherein one of R¹ and R² is -SR (wherein R is a 15C alkyl), and the other is a 15C alkyl or the like; A¹ and A⁴ are each 1,4-phenylene, trans-1,4-cyclohexylene or the like; Z₁ and Z₂ are each -CH₂CH₂-, -CH₂O- or the like; m and n are each 0 or 1; and A² and A³ are each 1,4-phenylene].

EXAMPLE: 4-Butylthio-4'-propyltolan.

USE: A liquid crystal phase component, especially suitable for use in a mixture for ECB(electrically controlled birefringency) effect.

PREPARATION: The corresponding stilbene is brominated, and the product is dehalogenated to obtain a compound of the formula.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following formula 1% Formula %() One of R1 and R2 represents -3R and the other represents an alkyl group having up to 15 carbon atoms, but one or more CH
The two groups are 10-, -CO-, -S-, -C1l-halogen-, -CHCN-, -0CO-, -COO-, or -C
It may also be replaced by H=CH-, in which case the two heteroatoms are not directly bonded to each other, R represents an alkyl group having up to 15 carbon atoms, and AI and A4 are each independent of each other. , unsubstituted or 1
1,4-phenylene substituted by one or more halogens and/or CH3 and/or CN, and of which one or more C)1 groups may be replaced by N, one or more non-adjacent CH2 groups represents trans-1,4-cyclohexylene or 1,4-bicyclo(2,2,2)octylene which may be replaced by 10- and/or -S- atoms, and Zl and Z2 are each independent of each other. -CH2CH2-
-CH20-, -0CH2, -CO-0--0-C0-
-CEC- or a single bond, m and n each independently represent O or 1, A2 and A3 are each independently unsubstituted or substituted by one or more halogen and/or CH3 and/or CN The present invention relates to tolan derivatives of the following formula, representing 1,4-phenylene, and their use as components of liquid crystal phases.

For simplicity, in the following specification, Phe represents an unsubstituted 1-4-phenylene group, and Ph
eX is one or more substituents (X is halogen and/or CL
and/or CN), Cyc is a trans-1,4-cyclohexylene group, Dio is a 1,3-dioxane-2,5-diyl group, and Pyd is a pyridine group. -2,5-diyl group, Py
r is pyrimidine-2,5-diyl group, Dit is 1-3
-dithian-2,5-diyl group, and Bco is 1.
4-bicyclo[2,2,2]octylene group.

The compound of the formula (III) is a component of liquid crystal phases for various display devices based on the principle of the so-called twisted cell, the guest/host effect, the effect of some ordered phase deformations or the effect of dynamic scattering. It can be used as

The compounds of formula I can also be used as components of liquid crystal phases, in particular for display devices based on the ECB effect.

Some similar compounds are e.g. British Patent Box 2, 155
．． 465A or French Patent Box 2.234.26
It is known from No. 1. However, these do not contain a 13R group as a terminal substituent.

The present invention was made with the object of finding mesogenic compounds suitable as new stable liquid crystals or as components of various liquid crystal phases. This object was achieved by providing compounds of formula 1 above.

It has been found that the compounds of formula I are eminently suitable as components of various liquid-crystalline phases. In particular, stable liquid crystal phases with relatively high optical anisotropy and significant negative dielectric anisotropy can be created with these compounds. The substances of formula I above are therefore particularly suitable for use in mixtures for ECB efficacy.

Regarding the ECB effect (the effect of electrically controlled birefringence) or also the DAP effect (the effect of the deformation of aligned phases),
First published in 1971 by M. F. 5chieckel and Fahrenschon, Appl.
Phys, Lett, 19°3912 (1971
) was described in ``Deformation in an electric field of a nematic liquid crystal with vertical alignment''. Subsequently, J. F. Kahn [
Appl, Phys, Lett, 20.1193 (19
72)], G, Labrunie and J, Rob
ert [J, Appl, Phys, 44.48
69 (1973)] was published.

J, Robert and F, C1erc [SID 80
Digest Techn.

Papers, 30 (1980)], Duchen, J.
e [Displays 7.3 (1986)] and H
,5chad[SID 82 Didest Tech
n.

Papers, 244 (1982)] showed that in order for various liquid crystal phases to be able to be used in highly informative display elements based on the ECB effect, high values of the elastic modulus ratio, optical It has been shown that the dielectric anisotropy Δn must have a high value and the dielectric anisotropy Δε a negative value.

Electro-optical display elements based on the ECB effect have a homeotropic end orientation, in other words their liquid crystal phase has negative dielectric anisotropy.

In order to utilize this effect industrially in electro-optical display elements, liquid crystal phases are required which must meet a number of requirements. Of particular importance here is chemical stability, for example against moisture, air and various physical influences, such as thermal radiation, radiation in the infrared, visible and ultraviolet ranges, and direct or alternating electric fields. A liquid-crystalline mesophase in a suitable temperature range and a low viscosity are additionally required for an industrially usable liquid-crystalline phase.

Surprisingly, it has been found that the addition of compounds of formula I above gives liquid crystal phases that meet the above-mentioned criteria eminently. Among these, it is advantageous that it has a lower viscosity than the corresponding oxygen compound (containing oxygen instead of sulfur).

By providing the compounds of the formula I, the range of different liquid-crystalline substances which are suitable from various technical points of view for the preparation of nematic mixtures is very generally considerably widened.

The compounds of formula I have a wide range of applications. Depending on the choice of substituents, these compounds can be used as base materials for constituting various liquid crystal phases; however, compounds of the above formula r can also be used as liquid crystal base materials for other types of compounds, e.g. for their dielectric properties. And/or it can also be added to optimize optical anisotropy. The compounds of formula I are also suitable as intermediate compounds for preparing other substances which can be used as components of various liquid-crystalline phases.

The compounds of formula I are colorless in their pure state and form various liquid-crystalline mesophases in temperature ranges convenient for electro-optical applications. They are very stable to chemicals, heat and light.

The invention thus relates to compounds of formula I as defined above and to methods of using these compounds as components of various liquid-crystalline phases. The present invention furthermore provides at least one of the formulas 1
It also relates to various liquid crystal phases containing compounds of the present invention and to various liquid crystal display elements, including electro-optic display elements, that include such phases.

In the above description and the following description, R1 and A in formula 1
I, Zl, m, A''A', Z2, A4, n and R2 shall have the meanings previously described unless otherwise specified.

Compounds of formula I thus include compounds of subformula Ia (containing two rings), subformulas Ib to Ie (containing three rings), and subformulas If to It (containing four rings) below.

R'-A2-C: C-A3-R” (I
aR'-A'-A"C=C-A'-R" (
I bR'-A2-CEC-A'-A'-R"
(I cR'-A'-Z'-A2-C=C-A'-R
” (r dR'-A2-CEC-A'-Z”-
A'-R" (I eRl-A'-A2-C=
C-A3-A'-R” (I fnR
'-A'-Z'-A'-CEC-A'-A'-82 (I
g) R'-A'-A"-CEC-A3-Z"-A'-R
” (Ih)R'-A'-Z'-A2-C= C-
A'-Z2-A'-R2 (I i) Among these, formula I
Particularly preferred are a, Ib, Ic, Id, Ie and If.

Preferred compounds of sub-formula Ia include compounds of sub-formulas Iaa to Iad below.

R'-Phe-C=C-Phe-SR(Iaa)R'
-PheX-C=C-Phe-SR(I ab)R'-
Phe-C=C-PheX-3R(Iac)R'-P
heX-C=C-PheX-3R (I ad) Among these, those of the formulas Iaa, Iab and Iac are particularly preferred.

Preferred compounds of sub-formula Ib and Ic are as follows:
a to Ibf are included.

RS-Phe-C=C-Phe-Cyc-R2(I b
a) R'-Phe-Phe-CmiC-Phe-5R(I
bb) R'-PheX-Phe-C= C-Phe-
3R(I bc)R3-PheX-C= C-Phe-
Cyc-R"(Ibd)R'-Pyd-Phe
-C=C-Phe-SR(I be)R'-Pyr-P
he-C=C-Phe-SR(Ibf) Among these, those of the formulas Iba, Ibb and Iad are particularly preferred.

Preferred compounds of sub-formula Id and Ie are sub-formula 1d below.
It includes compounds of a to Idh.

R'-A'-C) 12c) It-Phe-C=C-Ph
e-SR(I daRS-Phe-CE C-Phe-
QC) Iz-A'-R2(I dbRS-Phe-CE
C-Phe-OCO2-Phe-R2(I daR'-
Phe-CHzCL-Phe-CEC-Phe-SR(
IddR'-Cyc-CHzCH2-Phe-CEC-
Phe-3R(IdeR3-Phe-C=C-Phe-
OCO-A'-R2(I df)R'-A'-0CO-
Phe-C=C-PheX-3R(Idg)R'-A'
-CHzCHz-Phe-C= C-PheX-3R(
I dh) Among these are the formulas I dc, I dd,
Particularly preferred are those of Ide, Idf and Idg.

Preferred compounds of subformula If include compounds of subformula Ifa to Iff below.

R'-Phe-Phe-C=C-Phe-Phe-3R
(I fa)RS-Phe-Phe-C=C-Phe-
Cyc-R2(Ifb)RS-Phe-Phe-C=
C-Phe-Pyd-R2(I fc)R'-Pyr-
Phe-C=C-Phe-Phe-3R(I fd)R
'-Cyc-Phe-C=C-Phe-PheX-3R
(I fe)R'-Cyc-Phe-C=C-PheX
-Phe-SR(Iff) Among these, those of formulas Ifb and Iff are particularly preferred.

Preferred compounds of sub-formula Ig and Ih are as follows:
a to Igg compounds.

R'-Phe-CHzCH2-Phe-C=C-Phe
-Phe-SR(Iga) R3-PheX-Phe-C= C-Phe-CHzC
Hz-Cyc-R” (Igb) RS-Phe-CHzO-Phe-C=C-Phe-C
yc-R'' (Igc) R'-Cyc-PheX-CmiC-Phe-Phe-S
R(I gd)RS-A'-Phe-C=C-Phe-
OCO-A'-R2(Ige)R'-A'-Phe-C
=C-Phe-CHzO-A'-3R(Igf)R'-
A'-CH2CH2-Phe-C=C-A3-A'-3
Preferred compounds of R(Igg) sub-formula Ii include compounds of sub-formulas Iia to Iig below.

RS-Cyc-C)lzcHz-Phe-C=C-Ph
e-Z"-A'-R" (I 1a) R'-Pyd-CHzCHz-Phe-C=C-Phe
-Z2-A'-5R(Iib) R'-A'-COO-Phe-CE C-Phe-
2:2-A'-5R(IiC) R'-A'-COO-Phe-C= C-Phe-Z2
-PheX-3R(I 1d) R3-A'-CII20-A2-CEC-A'-Z2-
A'-R2(Iie) R3-A'-Z'-A2-C=C-A3-CH20-A
'-R2(Iif) R3-A'-Z'-PheX-CEC-A'-Z2-A
'-R'' (Iig) In the above formula and the formula listed below, one of R1 and R2 is -3R. In this -SR, R is an alkyl group having up to 15 carbon atoms. The alkyl chain may be linear or branched, preferably linear, and 1.2.3.4.5.6 or 7
carbon atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl, or also octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl or pentadecyl.

The other one of R' and R2 is preferably alkyl, akoxy or oxaalkyl or dioxaalkyl.

A1 and A4 are preferably 1,4-cyclohexylene or 1,4-phenylene containing halogen and/or CN
and/or CI (can be substituted by , 1.4-) If unicine is substituted, monosubstitution with fluorine or chlorine is preferred. AI and A4 are also preferably Bco, pyd or Dio.

Zl and Z2 are preferably a single bond or -C
H, C) There is 12-te. Further 1. NiGO-0- or -0-CO- are also preferred. Compounds in which Zl or Z2 is a triple bond of -CEC- are also preferred.

m and n are each independently the number O or 1, in which case m
+n is preferably 0 or 1.

A2 and A3 are preferably unsubstituted 1,4-phenylene. When A3 and A4 are substituted 1,4-phenylenes, mono-substitution with fluorine or chlorine is preferred, particularly preferably at the position ortho to R2 or R'.

However, the side substituents are also -C=C-3
It may be present in the ortho position with respect to the double bond.

However, one of A1, A2, A3 and A4 is 2.3
Also particularly preferred are compounds of formula 1 which are -dihalogeno-1,4-phenylene. In this case the halogen is fluorine, chlorine or bromine. 2.3-difluoro-1,4
-Phenylene is particularly preferred.

R1 or R2 is an alkyl group, and one of them is
of “alkoxy” or “oxaalkyl” or of two “
In case non-adjacent CH2 groups of "alkoxyalkoxy" or "dioxaalkyl" can also be substituted by oxygen, they can be linear or branched.

Preferably they are linear and 2.3.4.
having 5.6 or 7 carbon atoms, so they are preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy,
Pentoxy, hexoxy, heptoxy, 2-oxaprobyl (=methoxymethyl), 2-oxabutyl (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-3- or 4-oxapentyl, 2-3-1
4- or 5-oxahexyl or 2- 3- 4-
5- or 6-oxaheptyl, or further methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, tunoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecyl, pentadecyl, 2
- 3- 4- 5-16- or 7-oxaoctyl,
2- 3- 4- 5- 6-7- or 8-oxanonyl, 2-3-14-5- 6- 7- 8- or 9-oxadecyl, 1.3-dioxabutyl (=methoxymethoxy), 1.3 - 1.4- or 2,4-dioxapentyl, 1.3- 1.4-11.5-12.4-, 2
．． 5- or 3.5-dioxahexyl or 1.3-1
．． 4-1.5- 1.6-12.4- 2.5- 2.
63.5-13.6- or 4.6-dioxahebutyl.

Compounds of formula 1 with branched terminal substituents R1 or R2 may be important in some cases as they have good solubility in common liquid crystal base materials, but especially when they have optical activity, chiral doping substances It is useful as

Branching groups of this type generally have no more than one chain branch. Preferred branched groups are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (=3-
methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2
-octyl, isopropoxy, 2-methylpropoxy,
2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylhebutoxy (
=2-octyloxy), 2-year-old xar-3-methylbutyl, 3-year-old xar-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyl Octanoyloxy, 5-
They are methylhebutyloxy-carbonyl, 2-methylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl and 2-methyl-3-oxahexyl.

In the case of compounds with branched terminal substituents, formula I includes the optical antipodes and racemates as well as mixtures thereof.

Among the compounds of formula 1 and its dependent sub-formulas, preference is given to those compounds in which at least one group contained therein has one of the preferred meanings listed above.

A particularly preferred sub-group of compounds of formula (1) consists of the following partial carpenters to 16.

Alkyl-Phe-CEC-Phe-3R (1) Alkyl-Cyc-Phe-C=C-Phe-3R alkyl-
Phe-C=C-PheX-3R (5) Alkyl-Cy
c-Phe-C=C-PheX-3R(6) Alkyl-
Phe-C) I2C) I2-Phe-CE C"Phe
-SR alkyl-Phe-CH2CH2-Phe-C=
C-PheX-3Ralkyl-Phe-C)IzO-
Phe-C=C-Phe-3R(9)alkoxy-Ph
e-C=C-Phe-3R(10)alkoxy-Ph
e-Phe-C=C-Phe-SR (11) Alkoxy-Phe-CHzCHa-Phe-C=C-Phe-S
R alkyl-Pyd-Phe-C=C-Phe-3R(
15) Alkyl-Pyr-Phe-C=C-Phe-3
Compounds of formula (1) R (16) can be prepared by known methods as described in the literature (e.g.
Houben published by ThiemeVerlag
-Weyl's "Methodender Organi"
schen Chemie) under known and appropriate reaction conditions, particularly for this reaction. These reactions utilize various variants not detailed here. It is also possible.

If desired, each starting material can be formed as such, without being separated from the reaction mixture, for use immediately in subsequent reactions to form further compounds of formula (1).

Compounds of formula I can be made by brominating the corresponding stilbene and then dehydrohalogenating this product. It is also possible to use known modified methods for this reaction, which are not specifically described here.

These stilbene compounds can be made by reacting 4-substituted benzaldehydes with the corresponding phosphorus ylide compounds by the so-called Wittig method or by reacting 4-substituted phenylethylenes with the corresponding bromobenzene derivatives by the so-called Heck method. can.

Another possibility for creating a carbon-carbon triple bond is one which otherwise corresponds to formula T but contains a -CH2-Co- group instead of the 10=C- group. By reacting the compound with an inorganic acid chloride and dehydrohalogenating the formed -CH2-CCl□- group in the presence of a base, or alternatively, the above compound can be reacted with semicarbazide and selenium dioxide. It consists of reacting. The triple bond is then introduced by heating in the presence of methyllithium.

Furthermore, there is also the possibility of converting the corresponding benzyl derivatives into tolans by using hydrazine and subsequently using HgO.

Compounds of formula T can also be further represented by J, Org, Chem,
43.358 (197B), A, 0. King%E,N
egishi, F., J., Villani and A.
5 can also be made by coupling an alkynylzinc compound with an aryl halide by a method similar to that described by Ilveira.

Compounds of formula
Uttenberg-Wiechell rearrangement reaction [A
nn, 279.319°327, 332 (1984
) can also be made by rearranging a 1.1-diaryl-2-halogenethylene compound in the presence of a strong base to form a diarylacetylene.

Still further, compounds of formula (1) may be prepared from 4-substituted phenylacetylenes and aryl halides such as bis(triphenylphosphine)-palladium(II) chloride and iodized steel (
It is also possible to make it in the presence of a palladium catalyst such as I) [5ynthesis (1980) 627 or Tetrahedron Letters 27
1171 (1986).

In addition to the one or more compounds according to the invention described above, the liquid crystal phase according to the invention preferably has 2 to 40, especially 4 to 30
It further contains the following components as constituent elements. These phases particularly preferably contain, in addition to one or more compounds according to the invention, from 1 to 25 components. These other constituents are preferably various nematic and nematogenic (monotropic or isotropic) substances, in particular the following groups: azoxybenzene, benzylideneaniline, biphenyl, terphenyl, phenyl- or cyclohexylbenzoate, phenyl- or cyclohexylcyclohexanecarboxylate, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, benzoic acid, cyclohexylphenyl ester of cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexane, Cyclohexyl biphenyl, phenylcyclohexylcyclohexane, cyclohexylcyclohexane, cyclohexylcyclohexene, cyclohexylcyclohexylcyclohexene, 1
．． 4- and sucyclohexylbenzene, 4.4'- and sucyclohexylbiphenyl, phenylpyrimidine or cyclohexylpyrimidine, phenylpyridine or cyclohexylpyridine, phenyldioxane or cyclohexyldioxane, phenyl- or cyclohexyl- 1,3-dithiane, l,2-diphenylethane,
1.2-dicyclohexylethane, 1-phenyl-2-
Cyclohexylethane, l-cyclohexyl-2-(4
-phenyl-cyclohexyl)-ethane, 1-cyclohexyl-2-diphenylethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated stilbenes, benzylphenyl ethers, tolan compounds and substituted cinnamic acids. It is a compound selected from. In these compounds, 1,4-phenylene may be fluorinated.

The most important compounds suitable as further constituents of the liquid-crystalline phase according to the invention are those characterized by the following formulas 1, 2, 3, 4 and 5.

R'-L-E-R” I
R-L-COO-E-R” 2R
'-L-00C-E-R'' 3R
'-L-CF12CHt-E-R' 4
R'-L-C::C-E-R" 5 In the above formulas 1 to 5, each may be the same or different, and in each case, E independently represents the following group, i.e. -Phe--Cyc--Phe-P
he--Phe-Cyc--Cyc-Cyc--Pyr
-Dio--A divalent group selected from G-Phe- and -〇-Cyc- and their mirror images, where Phe is unsubstituted or substituted with fluorine, 1,4- Phenylene, Cyc is trans-1,4-
cyclohexylene or 1,4-cyclohexylene,
Pyr is pyrimidine-2,5-diyl or pyridine-
2,5-diyl, Dio is 1,3-dioxane-2,
5-diyl, and G is 2-(trans-1,4-cyclohexyl)-ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl. Representing each.

Preferably, one of L and E is Cyc, Phe or Pyr, and E is preferably Cyc, Pyr.
he or Phe-Cyc. The liquid crystal phase according to the present invention is preferably such that in the above formulas 1 to 5, L and E are CY
c, one or more components selected from compounds such as those selected from the group consisting of Phe and Pyr;
selected from the group consisting of he and Pyr, and the other is -
Phe-Phe-1-Phe-Cyc-1-Cyc-C
one or more components selected from the group consisting of yc-1-G-Phe- and -G-Cyc-, and optionally in the above formulas 1 to 5, where L and E are -Phe-Cyc-1-Cyc-Cyc-
It is preferable to include one or more compounds selected from the group consisting of 1-G-Phe- and -G-Cyc-.

In the compounds of sub-formulas 1a, 2a, 3a, 4a and 5a, Ro and R'' are in each case independently of one another alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of the compounds, Ro and R'' are different from each other, one of which is usually an alkyl or alkenyl group. Subformulas 1b, 2b, 3b.

In compounds 4b and 5b, R'' is -CN, -CFs
, F, Cfl or -NC3, in these compounds R has the same meaning as given for the compounds of sub-formulas 1a to 5a and is preferably alkyl or alkenyl. However, other variations of each of the above-mentioned substituents in compounds 1 to 5 above can also be used.

Many such substances or mixtures thereof are available commercially. All these compounds can be obtained by methods known in the literature or by analogous methods.

In addition to the components selected from the group of formulas 1a to 5a (group 1), the liquid crystal phase according to the invention can also contain components selected from the group of compounds of formulas 1b to 5b (group 2), Their proportions are then preferably as follows: Group 1: 20 to 90%, in particular 30 to 90% Group 2: 10 to 80%, in particular 10 to 50%, provided that the compounds according to the invention The sum of the proportions of the compounds of the first and second groups is 100%.

The liquid-crystalline phase according to the invention preferably contains 1 to 40%, particularly preferably 5 to 30%, of the respective compound according to the invention. more than 40%, in particular 45% of the compound according to the invention
Even more preferred are liquid crystal phases containing from 90% to 90%. These liquid crystal phases preferably contain 3 to 5 compounds according to the invention.

The liquid crystal phase according to the invention can be produced by conventional methods. Generally, the compounds are dissolved in each other, preferably at elevated temperatures. The liquid crystal phases according to the invention can be modified by suitable additives, so that they can be used in all types of liquid crystal display elements published to date. Such additives are well known to those skilled in the art and are well described in the literature (Elker/R, Hat elker/R, Hl, published by Verlag Chemie, Weinheim, 1980).
z'°' 1 (andbook of Liquid
For example, various substances can be added to change the dielectric anisotropy, viscosity and/or orientation of the nematic phase, or polychromatic dyes to create a colored guest/host system. .

[Examples] The present invention will be explained below using some examples, but the present invention is not limited to these in any way. In the following examples, M represents the melting point and C represents the clearing point. Furthermore, all percentages are by weight, and all temperatures are based on °C. Also, the term "process in the usual way" means adding water, extracting the mixture with methylene chloride, separating the organic phase,
This means drying and evaporating, then purifying the product by crystallization and/or chromatography.

On a large IL a) Add a few drops of bromine to a mixture of 250 mmol of magnesium ribbon and 60 mg of tetrahydrofuran (THF). Then 25% dissolved in THF at 50 m°C
A solution of 0 mmol of 4-bromo-1-butylthiobenzene is added. The mixture is stirred for about 30 minutes and a mixture of 200 mmol 4-acetylpropylbenzene and 25 mg THF is added to the Grignard reagent at 20-25'.

The mixture is stirred for 2 hours, poured into 500 mβ of water, acidified with concentrated hydrochloric acid and extracted with tert-butyl methyl ether (MTB ether). 120 mβ of 20% H2SO4 solution is added to the concentrated organic phase and the mixture is heated under reflux for 1 hour.

Purified by extraction with MTB ether, treatment of the organic phase and recrystallization from isopropanol to give 1-(p
-propylphenyl)-1-(p-butylthiophenyl)-ethylene is obtained.

b) 90 mmol of 1-(p-propylphenyl)-1
-(p-butylthiophenyl)-ethylene, 25mI2
of acetonitrile and 100 mC of CI (2C12) at about 0C, add 90 mmol of bromine at about 0C, stir the mixture for 1 hour and then add 90 mmol of triethylamine at 0-10C.Water is added, and The organic phase is separated and concentrated.The residue is heated to 130 m°C.
Pour into t-butanol, add 31.7 g of potassium tart-butyrate, and heat the mixture under reflux overnight. Add water and MTB ether,
The organic phase is then treated. 4 with M, = 65'' and C, = 20' (or more) by recrystallization from acetone.
-Butylthio-4'-propyltran is obtained.

The following compounds are prepared in a similar manner: 4-Methylthio 4'-pentylthiolane M, = 64
"C, = 51" (or more) 4-ethylthio-4'-pentyl-tolan 4-pro and Lunao 4° = pentylthio-4-butylthio-4'-pentyl-tolan 4-pentylthio-4°-benthylthio-tran 4-hexylthio-
4°-pentyl-tolan 4-hebutylthio-4°-benzitolan 4-methylthio-4°-methyl-tolan 4
-ethylthio-4°-methyl-tolan 4-pro and ruthio4' -methyl-tolan4-butylthio-4°-methyl-tolan4-pentylthio-4°-methyl-tolan4
-hexylthio-4°-methyl-tolan4-heptylthio-4°-methyl-tolan4-methylthio-4°-ethyl-tolan4-ethylthio-4°-dithirotolan4-
Propylthio-4'-ethyl-tran-4-butylthio-
4′-dithyltolan 4-pentylthio-4′-ethyl-tolan 4-hexylthio-4”-ethyl-tolan 4-
heptylthio-4°-ethyl-tran-4-methylthio-
4°-propyl-tolan 4-ethylthio-4′-propyl-tolan: M, = 84 @ C, = 30° (or more)
4-propylthio-4°-propyl-tolan 4-pentylthio-4°-propyl-tolan 4-hexylthio-4
°-Propyl-tolan 4-hebutylthio-4'-propyl-tolan 4-methylthio-4°-butyl-tolan 4-
Ethylthio-4'-butyl-tran-4-propylthio-
4°-Butyl-tran 4-butylthio-4″-butyl-
Tolan-4-pentylthio-4°-butyl-tolan-4-hexylthio-4'-butyl-tolan-4-hebutylthio-
4°-Butyl-tolan 4-methylthio-4’-hexyl-tolan 4-ethylthio-4°-hexyl-tolan 4-
Propylthio-4°-hexyl-tran 4-butylthio-4°-hexyl-tran 4-pentylthio-4″-hexyl-tran 4-hexylthio-4°-hexyl-tran 4-hebutylthio-4″-hexyl-tran 4-Methylthio-4°-heptyl-tolan 4-ethylthio-4
°-heptyl-tolan 4-propylthio-4°-heptyl-tolan 4-butylthio-4°-heptyl-tolan 4
-pentylthio-4°-hebutyl-tolan-4-hexylthio-4'-heptyl-tolan-4-hebutylthio-4°
-heptyl-tolan2,3-difluoro-4-methylthio-4'-butyl-tolan2,3-difluoro-4-ethylthio-4'-propyl-tolan2,3-difluoro-4-propylthio-4'-benchi Rootran 2. 3-Difluoro-4-butylthio-4°-propyl-tran Kuriyu Ia) Starting compound 4-bromothioanisole and 4-(trans-4-propylcyclohexyl)- in the same manner as in Example 1a. 1-(4-methylthiophenyl)-1-[4-(trans-propylcyclohexyl)phenyl]--ethylene is obtained from acetophenone.

b) 90 mmol of 1-(4-methylthiophenyl)-
1-[4-<trans-propylcyclohexyl)phenyl]-ethylene, 25 mfi of acetonitrile and 1
Add 90 mmol of bromine at Oo to a mixture of CH2Cl2 at 00 mC.

Subsequent operations were carried out in the same manner as in Example 1b, and after recrystallization from hexane, 4-methylthio-4°-(trans -4-propylcyclohexyl)-toran is obtained.

The following compounds are made in a similar manner: 4-Methylthio-4'-(1-trans-4-methylcyclohexyl)-tran 4-methylthio-4°-(trans-4-ethylcyclohexyl)-tran 4-methylthio- 4°-(trans-4-butylcyclohexyl)-tran 4-methylthio-4°-(trans-4-pentylcyclohexyl)-tran 4-methylthio-4”-(trans-4-hexylcyclohexyl)-tran 4- Methylthio-4°-(trans-4-hebutylcyclohexyl)-tran4-methylthio-4'-(trans-4-octylcyclohexyl)-tran4-ethylthio-4'-(trans-4-methylcyclohexyl)-tran 4-Ethylthio-4''-(trans-4-ethylcyclohexyl)-tran 4-ethylthio-4-(trans-4-propylcyclohexyl)-tran 4-ethylthio-4'-(trans-4-butylcyclohexyl)-tran 4-Ethylthio-4°-(trans-4-pentylcyclohexyl)-tran 4-ethylthio-4°-(trans-4-hexylcyclohexyl)-tran 4-ethylthio-4°-(trans-4-heptylcyclohexyl)- Tolan 4-ethylthio-4°-(trans-4-octylcyclohexyl)-tolan 4-propylthio-4°-(trans-4-methylcyclohexyl)-tolan 4-propylthio-4°-(trans-4-ethylcyclohexyl) -Tolan-4-propylthio-4°-(trans-4-propylcyclohexyl)-Tolan-4-propylthio-4°-(trans-4-butylcyclohexyl)-Tolan-4-propylthio-4°-(trans-4-pentylcyclohexyl) )-Toran-4-propylthio-4'-(trans-4-hexylcyclohexyl)-tolan-4-propylthio-4''-(trans-4-hef.

tylcyclohexyl)-tolan-4-propylthio-4°-(trans-4-octylcyclohexyl)-tolan-4-butylthio-4°-(trans-4-methylcyclohexyl)-tolan-4-butylthio-4'-D-trans-4 -ethylcyclohexyl)-tolan4-butylthio-4'-(trans-4-propylcyclohexyl)-tolan4-butylthio-4'-(trans-4-butylcyclohexyl)-tolan4-butylthio-4''-(trans- 4-pentylcyclohexyl)-tolan-4-butylthio-4'-(trans-4-hexylcyclohexyl)-tolan-4-butylthio-4°-(trans-4-hebutylcyclohexyl)-tolan-4-butylthio-4'- (trans-4-octylcyclohexyl)-tolan 4-pentylthio-4°-(trans-4-methylcyclohexyl)-tolan 4-pentylthio-4°-(trans-4-ethylcyclohexyl)-tolan 4-pentylthio-4° -(trans-4-propylcyclohexyl)-tolan 4-pentylthio-4"-(trans-4-butylcyclohexyl)-tolan 4-pentylthio-4°-(trans-4-pentylcyclohexyl)-tolan 4-pentylthio-4 ° -(trans-4-hexylcyclohexyl)-tran 4-pentylthio-4' -D trans-4-hebutylcyclohexyl)-tran 4-pentylthio-4' -(trans-4-octylcyclohexyl)-tran 4- Hexylthio-4°-(trans-4-methylcyclohexyl)-tran 4-hexylthio-4'-(trans-4-ethylcyclohexyl)-tran 4-hexylthio-4°-(trans-4-propylcyclohexyl) -Tolan 4-hexylthio-4°-(trans-4-butylcyclohexyl)-Tolan 4-hexylthio-4°-(trans-4-pentylcyclohexyl)-Tolan 4-hexylthio-4°-(trans-4 -hexylcyclohexyl)-tolan4-hexylthio-4'-(trans-4-heptylcyclohexyl)-tolan4-hebutylthio-4'-(trans-4-methylcyclohexyl)-tolan4-hebutylthio-4'' -(trans-4-ethylcyclohexyl)-tolan 4-hebutylthio-4° -(trans-4-propylcyclohexyl)-tolan 4-hebutylthio-4°-(trans-4-butylcyclohexyl)-tolan 4- Butylthio-4°-(trans-4-pentylcyclohexyl)-tolan-4-hebutylthio-4'-(trans-4-hexylcyclohexyl)-tolan-4-hebutylthio-4'-(trans-4-heptylcyclohexyl) -Tolan 2.3-difluoro-4-pro and ruthio 4'(trans-4-ethylcyclohexyl)-tolan 2.3-difluoro-4-propylthio-4°(trans-4-pentylcyclohexyl)-tolan 2.3 -difluoro-4-methylthio-4' -(trans-4-ethylcyclohexyl)-tolan2,3-difluoro-4-methylthio-4°-(trans-4-propylcyclohexyl)-tolan2,3-difluoro-4 -Butylthio-4'-(trans-4-propylcyclohexyl)-tolan2,3-difluoro-4-penteno1notio4(trans-4-ethylcyclohexyl)-tolan ME, 4hadana) Starting compound 4- Bromothioanisole and 1-(
4-Propylphenyl)-2-(4-acetylphenyl)-ethane [This converts 1-iodo-2-(4-propylphenyl)-ethane into 1-bromo-4-acetophenone ethylene ketal, magnesium and copper iodide. 1-(4-methylthiophenyl)-1-( 4-(4-propylphenylethyl)
-phenyl]-ethylene is obtained.

b) 4-Methylthio-4°-(4-probylphenylethyl)-tolan is obtained analogously to Example 1b from the product made in a) above.

The following compounds are made analogously: 4-Methylthio 4'-(4-methylphenylethyl)-tran 4-methylthio-4°-(4-ethylphenylethyl)
-Tolan4-methylthio-4'-(4-butylphenylethyl)-Tolan4-methylthio-4'-ethyl)-Tolan4-methylthio-4'-ethyl)-Tolan4-methylthio-4'-ethyl)- Tolan 4-ethylthio-4'- thyl)-tolan 4-ethylthio-4'- ethyl)-tolan 4-ethylthio-4'- ethyl)-tolan 4-ethylthio-4'- ethyl)-tolan 4-ethylthio-4 °-ethyl)-toran4-ethylthio-4°-ruethyl)-tolan4-ethylthio-4゛-(4-pentylphenyl(4-hexylphenyl(4-methylphenyl Propylphenyl(4-butylphenyle(4-pentylphenyl(4-hexylphenylethyl)-tolan-4-ethylthio-4′-ethyl)-tolan-4-ethylthio-4°-ethyl)-tolan-4-ethylthio-4° - ethyl)-tran 4-ethylthio-4'- ethyl)-tran 4-ethylthio-4''- nylethyl)-tran 4-ethylthio-4° - nylethyl)-tran 4-ethylthio-4° - nylethyl)-tran 4 -propylthio-4' ethyl)-tran 4-propylthio-4' ethyl)-tran 4-pro and ruthio 4° (4-methoxyphenyl (4-ethoxyphenyl) Fe(4-hexyloxyfe(4-heptyloxyphe(4-methylphenyl(4-ethylphenyl(4-pro-ruphenylethyl)-tran-4-propylthio-4゜ethyl)-tran-4-propylthio-4゛ethyl) -tolan-4-propylthio-4'-ethyl)-tolan-4-propylthio-4'-ethyl)-tolan-4-butylthio-4'-thyl)-tolan-4-butylthio-4'-thyl)-tolan-4-butylthio-4' - Ethyl)-tolan-4-butylthio-4°-thyl)-tolan-4-butylthio-4°-ethyl)-tolan-4-butylthio-4゛ - (4-butylphenyl(4-pentylthioni(4-hexylcife(4) -Heptylphenyl(4-methylphenyl(4-ethylphenyl)(4-propylphenyl(4-butylphenyl(4-pentylphenyl(4-hexylphenylethyl)-tran 4-butylthio-4°-(4 -hebutylphenylethyl)-tolan4-butylthio-4°-(4-methoxyphenylethyl)-tolan4-butylthio-4''-(4-ethoxyphenylethyl)-tolan4-butylthio-4'-(4- propoxyphenylethyl)-tolan 4-butylthio-4'-(4-butoxyphenylethyl)-tolan 4-butylthio-4°-(4-pentyloxyphenylethyl)-tolan 4-butylthio-4°-(4-to xyloxyphenylethyl)-tolan 4-butylthio-4' -(4-hebutyloxyphenylethyl)-tolan 4-pentylthio-4°-(4-methylphenylethyl)-tolan 4-pentylthio-4' -(4 -ethylphenylethyl)-tolan4-pentylthio-4°-(4-propylphenylethyl)-tolan4-pentylthio-4'-(4-butylphenylethyl)-tolan4-pentylthio-4''-(4-pentyl phenylethyl)-tolan4-pentylthio-4°-(4-hexylphenylethyl)-tolan4-pentylthio-4'-(4-hebutylphenylethyl)-tolan4-pentylthio-4°-(4-methoxy phenylethyl)-tolan4-pentylthio-4'-(4-ethoxyphenylethyl)-tolan4-pentylthio-4'-(4-propoxyphenylethyl)-tolan4-pentylthio-4'-(4-butoxyphenylethyl )-tolan 4-pentylthio-4°-(4-pentyloxyphenylethyl)-tolan 4-pentylthio-4'-(4-hexyloxyphenylethyl)-tolan 4-pentylthio-4'-(4-heptylthio (roxyphenylethyl)-tolan-4-hexylthio-4°-(4-methylphenylethyl)-tolan-4-hexylthio-4'-(4-ethylphenylethyl)-tolan-4-hexylthio-4'-(4 -propylphenylethyl)-tolan-4-hexylthio-4°-(4-)゛tylphenylethyl)-tolan-4-hexylthio-4° -(4-pentylphenylethyl)-tolan-4-hexylthio-4' -(4-hexylphenylethyl)-tolan 4-hexylthio-4°-(4-hebutylphenylethyl)-tolan 4-hebutylthio-4' -(4-methylphenylethyl)-tolan 4-hebutylthio -4°-(4-ethylphenylethyl)-tolan 4-hebutylthio-4°-(4-propylphenylethyl)-tolan 4-hebutylthio-4°-(4-butylphenylethyl)-tolan 4- Butylthio-4°-(4-pentylphenylethyl)-tolan4-hebutylthio-4'-(4-hexylphenylethyl)-tolan4-hebutylthio-4'-(4-heptylphenylethyl)-tolan4 -Methylthio-4°-(trans-4-methylcyclohexylethyl)-tran4-methylthio-4°-(trans-4-ethylcyclohexylethyl)-tolan4-methylthio-4°-(trans-4-propylcyclohexylethyl) )-tolan 4-methylthio-4°-(trans-4-butylcyclohexylethyl)-tolan 4-methylthio-4'-(trans-4-pentylcyclohexylethyl)-tolan 4-methylthio-4'-(trans-4 -hexylcyclohexylethyl)-tolan 4-methylthio-4°-(trans-4-hebutylcyclohexylethyl)-tolan 4-ethylthio-4'-(trans-4-methylcyclohexylethyl)-tolan 4-ethylthio-4 '-(trans-4-ethylcyclohexylethyl)-tran4-ethylthio-4'-(trans-4-propylcyclohexylethyl)-tran4-ethylthio-4'-(trans-4-butylcyclohexylethyl)-tran4 -Ethylthio-4°-(trans-4-pentylcyclohexylethyl)-tran4-ethylthio-4'-(trans-4-hexylcyclohexylethyl)-tran4-ethylthio-4°-(trans-4-hebutyl cyclohexylethyl)-tran 4-pro and ruthio 4'-(trans-4-methylcyclohexylethyl)-tran 4-propylthio-4°-(trans-4-ethylcyclohexylethyl)-tran 4-propylthio-4°-( trans-4-propylcyclohexylethyl)-tran 4-propylthio-4°-(trans-4-butylcyclohexylethyl)-tran 4-propylthio-4°-(trans-4-pentylcyclohexylethyl)-tran 4-pro and ruthio 4°-(trans-4-hexylcyclohexylethyl)-tran 4-propylthio-4'-(trans-4-heptylcyclohexylethyl)-tran 4-butylthio-4'-(trans-4-methylcyclohexylethyl) -Tolan-4-butylthio-4'-(trans-4-ethylcyclohexylethyl)-tolan-4-butylthio-4°-(trans-4-propylcyclohexylethyl)-tolan-4-butylthio-4°-(trans-4- butylcyclohexylethyl)-tolan-4-butylthio-4'-(trans-4-pentylcyclohexylethyl)-tolan-4-butylthio-4°-(trans-4-hexylcyclohexylethyl)-tolan-4-butylthio-4°-( trans-4-heptylcyclohexylethyl)-tran 4-pentylthio-4'-(trans-4-methylcyclohexylethyl)-tran 4-pentylthio-4°-(trans-4-ethylcyclohexylethyl)-tran 4-pentylthio- 4'-(trans-4-propylcyclohexylethyl)-tran 4-pentylthio-4'-(trans-4-butylcyclohexylethyl)-tran 4-pentylthio-4'-(trans-4-pentylcyclohexylethyl)-tran 4-Pentylthio-4'-(trans-4-hexylcyclohexylethyl)-tran 4-pentylthio-4°-(trans-4-heptylcyclohexylethyl)-tran 4-hexylthio-4°-(trans-4-methyl (cyclohexylethyl)-tolan-4-hexylthio-4°-(trans-4-ethylcyclohexylethyl)-tolan-4-hexylthio-4°-(trans-4-propylcyclohexylethyl)-tolan-4-hexylthio-4° -(trans-4-butylcyclohexylethyl)-tran 4-hexylthio-4°-(trans-4-pentylcyclohexylethyl)-tran 4-hexylthio-4'-(t-trans-4-hexylcyclohexylethyl )-tolan-4-hexylthio-4°-(trans-4-heptylcyclohexylethyl)-tolan-4-hebutylthio-4'-(trans-4-methylcyclohexylethyl)-tolan-4-hebutylthio-4'-D trans-4-ethylcyclohexylethyl)-tran 4-hebutylthio-4°-(trans-4-propylcyclohexylethyl)-tran 4-hebutylthio-4°-(trans-4-butylcyclohexylethyl)-tran 4- hebutylthio-4'-(trans-4-pentylcyclohexylethyl)-tran-4-hebutylthio-4°-(trans-4-hexylcyclohexylethyl)-tran-4-hebutylthio-4°-(trans-4-hef .

a) Analogously to Example 1a, 4-bromothioanisole and 4-propylbenzyl-(4-acetyl)-phenyl ether
-hydroxyacetophenone by reaction under basic conditions with ethylene ketal and subsequent cleavage of the ketal] from 1-methylthio-1-[
4-(4-propylbenzyloxy)phenylcoethylene is obtained.

b) The material prepared in a) above was reacted to give 4-methylthio-4 by the same reaction procedure as described in Example 1b.
°-(4-propylbenzyloxy)-tolan is obtained.

The following compounds are made in a similar manner.

4-Methylthio-4″-(4-methylbenzyloxy)-
Tran 4-methylthio-4°-(4-ethylbenzyloxy)
-tran 4-methylthio-4°-(4-butylbenzyloxy)-
Tolan 4-methylthio-4'-(4-pentylbenzyloxy)-tolan 4-methylthio-4'-(4-hexylbenzyloxy)-tolan 4-methylthio-4'-(4-hebutylbenzyloxy)- Tran 4-methylthio-4″-(4-octylbenzyloxy)
-Toran-4-ethylthio-4°-(4-methylbenzyloxy)-
Tran-4-ethylthio-4°-(4-ethylbenzyloxy)
-Toran-4-ethylthio-4°-(4-propylbenzyloxy)
-Toran-4-ethylthio-4°-(4-butylbenzyloxy)-
Tran 4-ethylthio-4″-(4-pentylbenzyloxy)
-Tolan-4-ethylthio-4'-(4-hexylbenzyloxy)-Tolan-4-ethylthio-4"-(4-hexylbenzyloxy)
-tran-4-propylthio-4°-(4-methylbenzyloxy)
-tran-4-propylthio-4°-(4-ethylbenzyloxy)
-Tolan4-propylthio-4'-(4-pro and rubenzyloxy)-tolan4-propylthio-4'-(4-butylbenzyloxy)-tolan4-propylthio-4'-(4-pentylbenzyloxy)-tolan 4-pro and ruthio 4°-(4-hexylbenzyloxy)-tran 4-propylthio-4'-(4-hebutylbenzyloxy)-tran 4-butylthio-4°-(4-methylbenzyloxy)-
Tran-4-butylthio-4°-(4-ethylbenzyloxy)-
Tran-4-butylthio-4°-(4-propylbenzyloxy)
-tran-4-butylthio-4' -(4-butylbenzyloxy)
-Tolan-4-butylthio-4'-(4-pentylbenzyloxy)-tolan-4-butylthio-4'-(4-hexylbenzyloxy)-tolan-4-butylthio-4°-(4-hebutylbenzyloxy)
-Tolan 4-pentylthio-4' -(4-methylbenzyloxy)-Tolan 4-pentylthio-4°-(4-ethylbenzyloxy)
-Tolan 4-pentylthio-4°-(4-propylbenzyloxy)-tolan 4-pentylthio-4' -(4-butylbenzyloxy)-tolan 4-pentylthio-4°-(4-pentylbenzyloxy)-tolan 4-Pentylthio-4'-(4-hexylbenzyloxy)-tolan 4-pentylthio-4°-(4-hebutylbenzyloxy)-tolan 4-hexylthio-4°-(4-methylbenzyloxy)
-tran-4-hexylthio-4'-(4-ethylbenzyloxy)
-Tolan-4-hexylthio-4°-(4-propylbenzyloxy)-Tolan-4-hexylthio-4'-(4-butylbenzyloxy)-Tolan-4-hexylthio-4''-(4-pentylbenzyloxy) )-tolan-4-hexylthio-4°-(4-hexylbenzyloxy)-tolan-4-hexylthio-4°-(4-hebutylbenzyloxy)-tolan-4-hebutylthio-4°-(4- methylbenzyloxy)-tolan-4-hebutylthio-4'-(4-ethylbenzyloxy)-tolan4-hebutylthio-4°-(4-propylbenzyloxy)-tolan4-hebutylthio-4'-(4 -butylbenzyloxy)-tolan 4-hebutylthio-4°-(4-pentylbenzyloxy)-tolan 4-hebutylthio-4'-(4-hexylbenzyloxy)-tolan 4-hebutylthio-4°- (4-Hebutylbenzyloxy)-tran 4-methylthio-4°-(4-methoxybenzyloxy)
-Tolan 4-methylthio-4° -(4-ethoxybenzyloxy)-Tolan 4-methylthio-4°-(4-propoxybenzyloxy)-Tolan 4-methylthio-4°-(4-butoxybenzyloxy)
-Tolan 4-methylthio-4° -(4-pentyloxybenzyloxy)-tolan 4-ethylthio-4' -(4-methoxybenzyloxy)-tolan 4-ethylthio-4°-(4-ethoxybenzyloxy)
-tran 4-ethylthio-4°-(4-propoxybenzyloxy)-tran 4-ethylthio-4゛-oxy)-tran 4-ethylthio-4°-siloxy)-tran 4-propylthio-4゜roxy)-tran 4-propylthio-4゜roxy)-toran-4-pro and ruthio-4'-siloxy)-toran-4-propylthio-4゜roxy)-toran-4-propylthio-4゜ndyloxy)-toran-4-butylthio-4'-xy) -tran 4-butylthio-4°-xy)-tran 4-butylthio-4°- -butoxybendi(4-pentyloxybe(4-methoxybencyl)(4-ethoxybencyl(4-propoxybenzyloxy)-toran 4-butylthio-4°-(4-butoxybenzyloxy)
-Tolan 4-butylthio-4°-(4-benzyloxybenzyloxy)-Tolan 4-pentylthio-4°-(4-methoxybenzyloxy)-Tolan 4-pentylthio-4°-(4-ethoxybenzyloxy)- Tolan 4-pentylthio-4”-(4-propoxybenzyloxy)-tolan 4-pentylthio-4°-(4-butoxybenzyloxy)-tolan 4-pentylthio-4°-(4-pentyloxybenzyloxy)-tolan 4-Methylthio-4°-(trans-4-methylcyclohexylmethyleneoxy)-tran 4-methylthio-4
°-(trans-4-ethylcyclohexylmethyleneoxy)-tran 4-methylthio-4°-(trans-4
-propylcyclohexylmethyleneoxy)-tran 4
-Methylthio-4°-(trans-4-butylcyclohexylmethyleneoxy)-tran 4-methylthio-4°
-(trans-4-pentylcyclohexylmethyleneoxy)-tran 4-methylthio-4' -(trans-
4-hexylcyclohexylmethyleneoxy)-toran4-methylthio-4°-(trans-4-to)ethylcyclohexylmethyleneoxy)-tolan4'-ethylthio-4°-(trans-4-methylcyclohexyl methyleneoxy)-tolan 4-ethylthio-4°-(trans-4-ethylcyclohexylmethyleneoxy)-tolan 4-ethylthio-4°-(trans-4-propylcyclohexylmethyleneoxy)-tolan 4-ethylthio-4' -(trans-4-butylcyclohexylmethyleneoxy)-tolan 4-ethylthio-4'-(trans-4-pentylcyclohexylmethyleneoxy)-tolan 4-ethylthio-4' -(trans-4-hexylcyclo xylmethyleneoxy)-tolan-4-ethylthio-4°-(trans-4-heptylcyclohexylmethyleneoxy)-tolan-4-propylthio-4°-
(trans-4-methylcyclohexylmethyleneoxy)-tran-4-propylthio-4'-D-trans-4-
ethylcyclohexylmethyleneoxy)-tran 4-pro and ruthio-4°-(trans-4-pro and cyclohexylmethyleneoxy)-tran 4-pro and ruthio 4
° -(trans-4-butylcyclohexylmethyleneoxy)-tran 4-propylthio-4° -(trans-4-pentylcyclohexylmethyleneoxy)-tolan 4-pro and ruthio 4' -D to trans-4- xylcyclohexylmethyleneoxy)-tolan-4-propylthio-4°-(trans-4-hebutylcyclohexylmethyleneoxy)-tolan-4-butylthio-4'-
(trans-4-methylcyclohexylmethyleneoxy)-tran-4-butylthio-4'-(trans-4-
ethylcyclohexylmethyleneoxy)-tolan-4-butylthio-4'-(trans-4-propylcyclohexylmethyleneoxy)-tolan-4-butylthio-4'
-(trans-4-butylcyclohexylmethyleneoxy)-tran-4-butylthio-4' -(1-trans-
4-pentylcyclohexylmethyleneoxy)-tolan-4-butylthio-4°-(trans-4-hexylcyclohexylmethyleneoxy)-tolan-4-butylthio-
4°-(trans-4-hebutylcyclohexylmethyleneoxy)-tran 4-pentylthio-4'-(trans-4-methylcyclohexylmethyleneoxy)-tran 4-pentylthio-4'-(trans-4-ethyl cyclohexylmethyleneoxy) ~tolan-4-pentylthio ~4°-(trans-4-propylcyclohexylmethyleneoxy)-tolan-4-pentylthio-4'-
(trans-4-butylcyclohexylmethyleneoxy)-tran 4-pentylthio-4'-(trans-4-
pentylcyclohexylmethyleneoxy)-toran 4-
Pentylthio-4'-(trans-4-hexylcyclohexylmethyleneoxy)-tran 4-pentylthio-4'-Dtrans-4-hebutylcyclohexylmethyleneoxy)-tran Example A Below: r-1-cyano -cis-4-(trans-4-propylcyclohexyl)-1-propylcyclohexane 14%l-(trans-4-
pro-cyclohexyl)-2-(2°-fluoro-4°-ethyl-biphenyl-4-yl)-nitane
2o% l-(trans-4-propylcyclohexyl)-2-(2°-fluoro-4′-bentelbiphenyl-4-yl)-ethane
19% 1-(trans-4-pentylcyclohexyl)-2-(2-fluoro-4'-dithylbiphenyl-4-yl)-ethane 2-fluoro-4,4°-bis-(trans-4-propyl) cyclohexyl)-biphenyl 2-fluoro-4-(trans-4-pentylcyclohexyl)-4°-(trans-4-propylcyclohexyl)-biphenyl 4-butyl-4°-ethoxy-tran 4-pentyl-4°-ethoxy- 17% 4% 5% 7% 4-Methylthio-4°-pentyl-tran
The liquid crystal phase consisting of 7% has a clearing point of 94°, △ε = -1,02 and △n = 0.1643
has.

Example B: r-1-cyano-cis-4-(trans-4-propylcyclohexyl)-1-pentylcyclohexane trans-1-p-methoxyphenyl-4-propylcyclohexane 2-fluoro-4,4'- Bis-(trans-4-propylcyclohexyl)-biphenyl 2-fluoro-4-(trans-4-pentylcyclohexyl)-4'-(trans-4-
(propylcyclohexyl)-biphenyl-4-propyl-4'-butyl-tolan-4-propyl-4'-benzitolan-4-butyl-4'-pentyl-tolan-4-methyl-4'-ethoxy-tolan-4-ethyl-4 °-Methoxy-tolan 4-methylthio-4°-(trans-4-propylcyclohexyl)-tolan 4-methylthio-4'-(trans-4-butylcyclohexyl)-
Tolan H% 10% 4% 5% 15% 13% 13% 5% 6% 6% 5% The liquid crystal phase consisting of 7% of 4-methylthio-4°-(trans-4-pentylcyclohexyl)-tolan has a clearing point of 76 °, △i = -0,45, △n=
Viscosity at 0.212 and 20° 20 mm”/se
It has c.

Claims (4)

[Claims] (1) The following formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) One of R^1 and R^2 represents -SR, and the other represents an alkyl group having up to 15 carbon atoms, but One or more CH_2 groups may be replaced by -O-, -CO-, -S-, -CH-halogen-, -CHCN-, -OCO-, -COO-, or -CH=CH-, In this case, the two heteroatoms are not directly bonded to each other, and R is 1
represents an alkyl group having up to 5 carbon atoms, A^1 and A^4 are each independently of one another unsubstituted or one or more halogens and/or CH_3 and/or C
substituted by N, and one or more CH groups are substituted by N
1,4-phenylene which may be replaced by 1,4-phenylene, trans-1,4-cyclohexylene which may have one or more non-adjacent CH_2 groups replaced by -O- and/or -S- atoms, or 1 ,4-bicyclo(2,2,2)octylene, and Z^1 and Z^2 each independently represent -CH_2C
H_2-, -CH_2O-, -OCH_2, -CO-O
-, -O-CO-, -C≡C- or a single bond, m and n each independently represent 0 or 1, A^2 and A^3 each independently represent an unsubstituted or 1 three or more halogens and/or CH_3 and/or CN
A tolan derivative represented by: 1,4-phenylene substituted by (2) A liquid crystal phase containing at least two liquid crystal components, the liquid crystal phase containing at least one compound of formula 1 according to claim 1. (3) A liquid crystal phase containing the compound of formula I according to claim 1 as a liquid crystal component. (4) An electro-optical display element comprising the liquid crystal phase according to claim 2 as a liquid crystal dielectric.