DE3734332A1 - Heterocyclic liquid-crystal compounds - Google Patents

Abstract

Heterocyclic liquid-crystal compounds containing the structural unit <IMAGE> in which M is H, CN, NCS, halogen or an alkyl group having 1-5 carbon atoms, X is CR<4> or N, Y is CHR<4>, O, S or NR<5>, R<4> is H, alkyl having 1-15 carbon atoms, halogen or cyano, and R<5> is H or alkyl having 1-15 carbon atoms, with the proviso that, in the case of Y = CHR<4>, X is N, are suitable as components of liquid-crystalline phases.

Description

The invention relates to heterocyclic liquid crystals connections that the structural element A

included in what

MH, CN, NCS, halogen or an alkyl group with 1-5 C atoms,
X CR⁴ or N,
Y CHR⁴, O, S or NR⁵,
R⁴ H, alkyl with 1-15 C atoms, halogen or cyan and
R⁵ is H or alkyl with 1-15 C atoms,

with the proviso that in the case of Y = CHR⁴

X means N.

For the sake of simplicity, Cy in the following means one 1,4-cyclohexylene group, dio a 1,3-dioxane-2,5-diyl group, Dit a 1,3-dithiane-2,5-diyl group, Bi one 1,4-bicyclo (2,2,2) octylene group, pip a piperidine-1,4- diyl group, Phe a 1,4-penylene group, Pyr a Pyri midin-2,5-diyl group and Pyn a pyridazine-3,6-diyl group, wherein Cy and / or Phe and / or Pyr and / or Pyn unsubstituted or by one or more F and / or Cl atoms and / or CH₃ groups and / or CN groups substituted could be. Dec also means a decahydronaph thalin-2,6-diyl group and Tet a 1,2,3,4-tetrahydro naphthalene-2,6-diyl group, where Dec and / or Tet unsub may be substituted or substituted by CN.

The compounds containing the structural element A can used as components of liquid crystalline phases be, especially for displays based on the principle the twisted cell, the guest-host effect, the effect the deformation of erected phases, the effect of dynamic scattering or the SSFLC principle.

The invention was based, new stable task find liquid-crystalline or mesogenic compounds, the as components of liquid crystalline phases are suitable.

It has been found that liquid crystal compounds containing the structural element A, as components liquid crystalline phases are particularly suitable. In particular are stable liquid-crystalline phases with their help with a wide mesophase range and comparatively lower Viscosity can be produced.

Liquid crystal compounds are said to be above and below such connections are understood that in themselves  are liquid crystalline, but also those compounds form the monotropic phases and thus as additives are of great importance for liquid crystal mixtures.

Furthermore, the compounds of the formula I contain the structural element A, through particularly advantageous Values for the ratio of the elastic constants.

With the provision of the compounds of formula I will also generally the range of liquid crystalline Substances that are under different application technical aspects for the production liquid crystalline mixtures are suitable, considerably broadened.

The compounds of formula I have a wide range Scope of application. Depending on the selection of the Substituents can use these compounds as base materials serve from which liquid crystalline phases are composed for the most part; it can but also compounds of formula I liquid crystalline Base materials from other classes of compounds added to, for example, the dielectric and / or optical anisotropy of such a dielectric to influence. The compounds of formula I are suitable themselves as intermediates for the manufacture of others Substances that are components of liquid crystalline Have dielectrics used.

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

The invention thus relates to heterocyclic Liquid crystal compounds containing structural element A. The invention also relates to heterocyclic Connections of the structure

Wing group ring (bridge link ring) _(1-3) wing group,

wherein at least one ring represents the structural element A. This structure represents the typical structure of liquid represent crystal connections. Here come for the wings groups, rings and bridge links all, the specialist known, structural elements in question. Quite a number of such suitable wing groups, rings and bridges structure is from D. Demus et al. in "Liquid Crystals in tables ", VEB German publishing house for basic material industry, Leipzig 1984. Under wing group, ring and pontic should be here not only those mentioned above Elements described in the literature, but also similar structures that are suitable be understood.

The invention furthermore relates to heterocyclic Compounds of formula I.

R¹-A¹-Z¹-A²-R² (I)

wherein

R¹ and R² each independently represent an un-substituted or substituted alkyl group with 1-15 C atoms, in which one or more CH₂ groups are also formed by a group from the group -O-, -CO-, -CH-halogen-, - CHCN-, -O-CO-, -CO-O- and -CH = CH- or can be replaced by a suitable combination of two groups, two heteroatoms not being directly linked to one another, one of the radicals R¹ and R² also H, F, Cl, BR, -CN, -NCS or R³- (A³) _p -Z²-,
A¹ -A-, -A⁴-Z³-A- or -A-Z³-A⁴-,
A², A³ and A⁴ are each 1,4-phenylene which is unsubstituted or substituted by one or more F and / or Cl atoms and / or CH₃ groups and / or CN groups, in which also one or two CH groups are substituted by N- Atoms can be replaced, 1,4-cyclohexylene, in which one or two non-adjacent CH₂ groups can also be replaced by O atoms and / or S atoms, piperidine-1,4-diyl, 1,4-bicylo (2nd , 2,2) octylene, unsubstituted or CN-substituted decahydro naphthalene-2,6-diyl or 1,2,3,4-tetra hydronaphthalene-2,6-diyl,
Z¹, Z² and Z³ each -CO-O, O-CO-, -OCH₂-, -CH₂O-, -CH₂CH₂- substituted ethylene or a single bond,
R³ H, an unsubstituted or substituted alkyl group with 1-15 C atoms, in which also one or more CH₂ groups by a group from the group -O-, -CO-, -CH-halogen-, -CHCN-, -O -CO-, -CO-O and -CH = CH- or can be replaced by a suitable combination of two groups, two heteroatoms not being directly linked to one another, F, Cl, Br, -NCS or -CN,
p 1 or 2, and
A the structural element

is in what

MH, CN, NCS, halogen or an alkyl group with 1-5 C atoms,
X CR⁴ or N,
Y CHR⁴, O, S or NR⁵,
R⁴ H, alkyl with 1-15 C atoms, halogen or cyan and
R⁵ is H or alkyl with 1-15 C atoms,

where for p = 2 the groups A³ may be the same or different, with the proviso that in the case of Y = CHR⁴ means XN.

The invention also relates to the use of these heterocyclic liquid crystal compounds as compo nenten liquid-crystalline phases. Also subject of the invention liquid-crystalline phases with a content on at least one compound according to the invention and electro-optical display elements, such phases contain.  

Above and below, R¹, R², R³, A¹, A², A³, A⁴, A, Z¹ and Z² have the meaning given, unless stated otherwise something else is expressly noted.

The compounds of formula I accordingly include Compounds of sub-formulas Ia to Iay:

R¹-A-Z¹-A²-R² (Ia)
R¹-A-A²-R² (Ib)
R¹-A⁴-Z³-A-Z¹-A²-R² (Ic)
R¹-A⁴-A-A²-R² (Id)
R¹-A⁴-A-Z¹-A²-R² (Ie)
R¹-A⁴-Z³-A-A²-R² (If)
R¹-A-Z¹-A²-Z²-A³-R³ (Ig)
R¹-A-A⁴-A²-R² (Ih)
R¹-A-Z³-A⁴-A²-R² (Ii)
R¹-A-A²-Z²-A³-R³ (Ij)
R³-A³-A³-Z²-A-Z¹-A²-R² (Ik)
R³-A³-A⁴-Z³-A-Z¹-A²-R² (Il)
R³-A³-A³-Z²-A-A²-R² (Im)
R³-A³-A⁴-A-A²-R² (In)
R³-A³-A³-A-Z¹-A²-R² (Io)
R¹-A-Z¹-A²-Z²-A³-A³-R³ (Ip)
R¹-A-A²-A³-A³-R³ (Iq)
R¹-A-Z¹-A²-A³-A³-R³ (Ir)
R¹-A-A²-Z²-A³-A³-R³ (Is)
R³-A³-Z²-A⁴-Z³-A-Z¹-A²-R² (It)
R¹-A⁴-A-Z¹-A²-Z²-A³-R³ (Iu)
R³-A³-Z²-A⁴-A-Z¹-A²-R³ (Iv)
R¹-A⁴-A-A²-Z²-A³-R³ (Iw)
R¹-A-Z³-A⁴-Z¹-A²-Z²-A³-R³ (Ix)
R¹-A-Z³-A⁴-A²-Z²-A³-R³ (Iy)
R¹-A-A⁴-Z¹-A²-Z²-A³-R³ (Iz)
R¹-A-A⁴-A²-Z²-A³-R³ (Iaa)
R¹-A-Z³-A⁴-Z¹-A²-Z²-A³-A³-R³ (Iab)
R¹-A-Z³-A⁴-Z¹-A²-A³-A³-R³ (Iac)
R¹-A-Z³-A⁴-A²-Z²-A³-A³-R³ (Iad)
R¹-A-A⁴-Z¹-A²-Z²-A³-A³-R³ (Iae)
R¹-A-A⁴-A²-A³-A³-R³ (Iaf)
R¹-A-Z³-A⁴-A²-A³-A³-R³ (Iag)
R¹-A-A⁴-Z¹-A²-A³-A³-R³ (Iah)
R¹-A-A⁴-A²-Z²-A³-A³-R³ (Iai)
R³-A³-A³-Z²-A⁴-Z³-A-Z¹-A²-R² (Iaj)
R¹-A⁴-Z³-A-Z¹-A²-A³-A³-R³ (Iak)
R¹-A⁴-Z³-A-A²-Z²-A³-A³-R³ (Ial)
R¹-A⁴-A-Z¹-A²-Z²-A³-A³-R³ (Iam)
R³-A³-A³-A⁴-A-A²-R² (Ian)
R¹-A⁴-A-A²-Z²-A³-A³-R³ (Iao)
R¹-A⁴-Z³-A-A²-A³-A³-R³ (Iap)
R³-A³-A³-A⁴-Z³-A-A²-R² (Iaq)
R³-A³-A³-A-A⁴-A²-R² (Iar)
R³-A³-A³-Z²-A-Z³-A⁴-Z¹-A²-R² (Ias)
R³-A³-A³-Z²-A-A⁴-Z¹-A²-R² (Iat)
R³-A³-A³-Z²-A-Z³-A⁴-A²-R² (Iau)
R³-A³-A³-A-Z³-A⁴-Z¹-A²-R² (Iav)
R³-A³-A³-Z²-A-A⁴-A²-R² (Iaw)
R³-A³-A³-A-Z³-A⁴-A²-R² (Iax)
R³-A³-A³-A-A⁴-Z¹-A²-R² (Iay)

The compounds of the sub-formulas Ia, Ib, Ie, If, Ii, Ij, Im, Ir, Is or Iy are preferred.

In the compounds of the formulas above and below R¹, R² and R³ are preferably alkyl or alkoxy.

Preference is also given to compounds before and after standing formulas in which one of the radicals R¹, R² and R³ means CN, F or Cl.  

A², A³ and A⁴ are preferably unsubstituted or mono- or polysubstituted 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl. Mono substitution is preferred for substituted groups. F, Cl, CH₃ or CN are suitable as substituents. The preferred substituent is fluorine. p is preferably 1.

Z¹, Z² and Z³ are preferably single bonds, in the second Line preferably -CO-O- or -O-CH₂- and the corresponding reverse groups or -CH₂CH₂ groups. This ethylene Groups can also be substituted and correspond then preferably the group -CHR⁶-CH₂-, wherein the substituent R⁶ is a halogen atom, a CN group or an alkyl group with up to 5 carbon atoms. R⁶ is preferred F, Cl, CH₃ or CN.

If R¹ and / or R² or R³ alkyl radicals and / or alkoxy mean residues, they can be straight-chain or branched be. They are preferably straight-chain, have 2, 3, 4, 5, 6 or 7 carbon atoms and are therefore preferably ethyl, Propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, Butoxy, pentoxy, hexoxy or heptoxy, also methyl, Octyl, nonyl, decyl, undexyl, dodexyl, tridecyl, tetra decyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, Undecoxy, dodecoxy, tridecoxy or tetradexocy.

Compounds of the formula I with branched wing groups R¹, R² or R³ can occasionally be used for better Solubility in the usual liquid crystalline base materials are important, but especially as chiral dopants if they are optically active.

Branched groups of this type usually contain no more than a chain branch. Preferred branched R¹, R² or R³ are isopropyl, 2-butyl  (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methyl butyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, Isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methyl butoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhoxoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxy-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methyl heptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl, 2-methyl 3-oxahexyl, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryl oxy.

In structural element A, X means CR⁴ or N. Y means CHR⁴, O, S or NR⁵, preferably S, O or NR⁵.

R⁵ is H, alkyl with 1-15 C atoms, halogen or cyan, preferably H or alkyl with 1-7 C atoms. R⁵ is hiring H atom or an alkyl group with 1-15, preferably with 1-7 carbon atoms.

If Y is CHR⁴, X means N.

The substituent M can be a CN or NCS group Halogen atom, an H atom or an alkyl group with 1-5 carbon atoms. M is preferably H, CN or one Alkyl group. Of the halogen atoms are F, Cl, Br, J F and Cl preferred.  

The following formulas (1) to (7) are preferred representatives of structural element A:

The structural elements (3) and are particularly preferred (6).

M has the meaning given in the formulas (1) - (7). M is preferably in the 5 position, but can also be in Position 4 or 6.

The compounds of formula I are known per se Methods produced as described in the literature (e.g. in the standard works such as Houben-Weyl, methods  of organic chemistry, Georg-Thieme-Verlag, Stuttgart) are described, namely under reaction conditions, known and suitable for the above-mentioned implementations are. You can also from well-known, here make use of variants not mentioned in more detail.

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

The compounds of the formula I can be prepared in this way by making a connection that is otherwise the Formula I corresponds, but instead of H atoms one or more reducible groups and / or C-C bonds contains, reduced.

Carbonyl are preferred as reducible groups groups into consideration, especially keto groups e.g. B. free or esterified hydroxyl groups or aromatic bonded halogen atoms. Preferred starting materials for the Reduction correspond to Formula I, but can be in place a cyclohexane ring a cyclohexene ring or cyclo hexanone ring and / or in place of a -CH₂CH₂ group -CH = CH group and / or instead of a -CH₂ group one -CO group and / or a free one instead of an H atom or one functional (e.g. in the form of its p-toluenesulfonate) modified OH group included.

The reduction can e.g. B. done by catalytic Hydrogenation at temperatures between about 0 ° and about 200 ° C and pressures between about 1 and 200 bar in an inert solvent, e.g. B. an alcohol like 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. As catalysts are suitable precious metals such as Pt or Pd, in the form of oxides (e.g. PtO₂, PdO), on one Carrier (e.g. Pd on carbon, calcium carbonate or strontium carbonate) or used in finely divided form can be.

Ketones can also be prepared using Clemmensen's methods (with Zinc, amalgamated zinc or tin and hydrochloric acid, useful in aqueous-alcoholic solution or in heterogeneous Phase with water / toluene at temperatures between about 80 and 120 ° C) or Wolff-Kishner (with hydrazine, purpose moderately in the presence of alkali such as KOH or NaOH in one high-boiling solvents such as diethylene glycol or Triethylene glycol at temperatures between about 100 and 200 ° C) to the corresponding compounds of formula I, which contain alkyl groups and / or -CH₂CH₂ bridges, be reduced.

Reductions with complex hydrides are also possible. For example, arylsulfonyloxy groups with LiAlH₄ be removed reductively, especially p-toluene sulfonyloxymethyl groups are reduced to methyl groups, appropriately in an inert solvent such as diethyl ether or THF at temperatures between about 0 and 100 ° C. Double bonds can (even in the presence of CN groups!) With NaBH₄ or tributyltin hydride in Methanol are hydrogenated.

By cyclization of corresponding thiophene, furan or pyrrole compounds in the 3-position by propion acid derivatives are substituted, the structure elements A can be produced particularly advantageously. The  Cyclization takes place according to methods known per se, e.g. B. on the corresponding acid chlorides, anhydrides or reactive esters, preferably in an inert solution medium.

Another advantageous method for producing the Structural element A consists of thiophene, thiazole, Oxazole, pyrrole, furan or imidazole-2,3-dicarboxylic acid to cyclize esters. First, the carbonyl groups reduced. The ring closure to the cyclopentane ring then takes place via the corresponding tosylate by reaction with malonic ester according to processes known per se.

Esters of the formula I can also be esterified corresponding carboxylic acids (or their reaction capable derivatives) with alcohols or phenols (or their reactive derivatives) will.

As reactive derivatives of the carboxylic acids mentioned the acid halides are particularly suitable the chlorides and bromides, furthermore the anhydrides, e.g. B. also mixed anhydrides, azides or esters, in particular Alkyl esters with 1-4 C atoms in the alkyl group.

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

The esterification is advantageous in the presence of a inert solvent performed. Are well suited in particular ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid  hexamethyltriamide, hydrocarbons such as benzene, Toluene or xylene, halogenated hydrocarbons such as tetra chlorinated carbon or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfolane. Not with water Miscible solvents can be beneficial at the same time for azeotropically distilling off during esterification formed water can be used. Occasionally can also an excess of an organic base, e.g. B. pyridine, Quinoline or triethylamine as a solvent for the Esterification can be applied. The esterification can also in the absence of a solvent, e.g. B. by simple Heating the components in the presence of sodium acetate. The reaction temperature is usually between -50 ° and + 250 ° C, preferably between -20 ° and + 80 ° C. Are at these temperatures the esterification reactions usually after 15 minutes ended up to 48 hours.

In particular, the reaction conditions depend on the Esterification largely depends on the nature of the used Starting materials. So is a free carboxylic acid a free alcohol or phenol usually in the presence a strong acid, for example one Mineral acid such as hydrochloric acid or sulfuric acid. A preferred mode of reaction is implementation an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in one basic environment, with alkali in particular as bases metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, 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  are. Another preferred embodiment of the Esterification consists in that the alcohol or the phenol first in the sodium or potassium alcoholate or -phenolate transferred, e.g. B. by treatment with ethanolic sodium or potassium hydroxide solution, this isolated and together with sodium bicarbonate or Potassium carbonate with stirring in acetone or diethyl ether suspended and this suspension with a Solution of acid chloride or anhydride in diethyl ether, acetone or DMF added, expediently at temperatures between about -25 and + 20 ° C.

For the preparation of nitriles of formula I (wherein R¹, R² or R³ is CN and / or wherein A², A³ and / or A⁴ is substituted by at least one CN group) corresponding acid amides can be hydrated. The amides are e.g. B. from corresponding esters or Acid halides obtainable by reaction with ammonia. Suitable as water-releasing agents are, for example wise inorganic acid chlorides such as SOCl₂, PCl₃, PCl₅, POCl₃, SO₂Cl₂, COCl₂, further P₂O₅, P₂S₅, AlCl₃ (z. B. as Double compound with NaCl), aromatic sulfonic acids and Sulfonic acid halides. You can do it in the present or Absence of an inert solvent at temperatures work between about 0 ° and 150 ° C; as a solvent come z. B. 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 can also be acid halides, preferably the chlorides, react with sulfamide, appropriately in an inert solvent such as tetra  methylene sulfone at temperatures between about 80 ° and 150 ° C, preferably at 120 °. After usual work-up you can isolate the nitriles directly.

Ethers of formula I (wherein R¹ and / or R² and / or R³ represents an alkoxy group and / or wherein Z 1 and / or Z² and / or Z³ is a -OCH₂-- or a -CH₂O - group) are by etherification of corresponding hydroxy compounds, preferably corresponding phenols, available, wherein the hydroxy compound expediently first in a ent speaking metal derivative, e.g. B. by treatment with NaH, NaNH₂, NaOH, KOH, Na₂CO₃ or K₂CO₃ in the ent speaking alkali metal alcoholate or alkali metal phenolate is transferred. This can then be done with the corresponding alkyl halide, sulfonate or dialkyl sulfate are implemented, advantageously in an inert Solvents such as acetone, 1,2-dimethoxyethane, DMF or Dimethyl sulfoxide or an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 ° C.

For the preparation of nitriles of formula I (wherein R¹, R² or R³ is CN and / or wherein A², A³ and / or A⁴ is substituted by at least one CN group) can also corresponding chlorine or bromine compounds of the formula I are reacted with a cyanide, appropriately with a metal cyanide such as NaCN, KCN or Cu₂ (CN) ₂, e.g. B. in the presence of pyridine in an inert solution medium like DMF or N-methylpyrrolidone at temperatures between 20 ° and 200 ° C.

Compounds of formula I, wherein R¹ or R² or R³ F, Cl, Br or CN can also mean from the corresponding diazonium salts by exchanging the dia  zonium group against a fluorine, chlorine or bromine atom or against a CN group, e.g. B. using Schiemann methods or Sandmeyer.

The diazonium salts are e.g. B. producible by nitriding of compounds corresponding to formula I, however Place one or two of the radicals R¹ or R² or R³ contain atom (s), reduction to the corresponding Amines and diazotization, for example with NaNO₂ or KNO₂ in aqueous solution at temperatures between about -10 and + 10 ° C.

The diazonium group can be replaced by fluorine and diazotize in anhydrous hydrofluoric acid then heat, or you can sit with tetrafluor boric acid to the diazonium tetrafluoroborates, which are then thermally decomposed.

An exchange for Cl, Br or CN is successful by reaction of the aqueous diazonium salt solution with Cu₂Cl₂, Cu₂Br₂ or Cu₂ (CN) ₂ according to the method of Sandmeyer.

The liquid-crystalline phases according to the invention consist of 2 to 25, preferably 3 to 15 components, including at least one liquid crystal compound containing the structural element A or one Compound of formula I. The other ingredients are preferably selected from the nematic or nematogenic substances, especially the known ones Substances from the classes of azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl or Cyclohexylbenzoate, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclo  hexylbiphenyls, cyclohexylcyclohexanes, cyclohexyl naphthalenes, 1,4-bis-cyclohexylbenzenes, 4,4′-bis- cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, Phenyl or cyclohexyl dioxanes, phenyl or Cyclohexyldithiane, 1,2-bis-phenylethane, 1,2-bis cyclohexylethane, 1-phenyl-2-cyclohexylethane if halogenated stilbene, benzylphenyl ether, Tolanes and substituted cinnamic acids.

The main as components of such liquid crystalline phases in question compounds can be characterized by Formula II,

R′-L-G-E-R ′ ′ (II)

where L and E each have a carbocyclic or heterocyclic ring system from that from 1,4-disubstituted benzene and Cyclohexane rings, 4,4′-disubstituted biphenyl, Phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydro naphthalene, quinazoline and tetrahydroquinazoline Group,

G-CH = CH-
-CH = CY-
-C = C-
-CO-O-
-CO-S-
-CH = N-
-N (O) = N-
-CH = N (O) -
-CH₂-CH₂-
-CH₂-O-
-CH₂-S-
-COO-Phe-COO-

or a C-C single bond, Y halogen, preferably Chlorine, or -CN, and R 'and R' 'alkyl, alkoxy, alkanoyl  oxy or alkoxycarbonyloxy with up to 18, preferably up to 8 carbon atoms, or one of these residues also mean CN, NC, NO₂, CF₃, F, Cl or Br.

Most of these compounds are R ′ and R ′ ′ different from one another, one of these residues mostly is an alkyl or alkoxy group. But others too Variants of the proposed substituents are common. Many such substances or mixtures thereof are commercially available. All of these substances are can be produced by methods known from the literature.

The liquid-crystalline phases according to the invention contain about 0.1 to 99, preferably 10 to 95%, one or more compounds containing the structural element A or one or more compounds of Formula I. Also preferred are liquid crystalline Phases that are 0.1-50, especially 0.5-30% or contain several compounds according to the invention.

Compounds of formula I with an optically active wing group are suitable as components of nematic liquid crystalline phases to avoid reverse twist and to improve the elastic constants.

Furthermore, the optically active compounds of formula I also as components of chirally tilted smectic liquid crystalline phases suitable.

These phases are included in the achiral base mixture in addition to chiral compounds of formula I at least one other component with a negative or smaller amount positive dielectric anisotropy.  

As further components with negative dielectric Anisotropy are suitable compounds containing the Structural element A, B or C.

Preferred compounds of this type correspond to the Formulas IVa, IVb and IVc:

R 'and R' 'each preferably represent straight-chain Alkyl or alkoxy groups, each with 2 to 10 carbon atoms. Q¹ and Q² each represent 1,4-phenylene, trans-1,4-cyclo hexylene, 4,4'-biphenylyl, 4- (trans-4-cyclohexyl) phenyl, trans, trans-4,4'-bicyclohexyl or one of the groups Q¹ and Q² also a single bond.

Q³ and Q⁴ each represent 1,4-phenylene, 4,4'-biphenylyl or trans-1,4-cyclohexylene. One of the groups Q³ and Q⁴ can also mean 1,4-phenylene, in which at least one CH group is replaced by N. R '' 'is an optical active residue with an asymmetric carbon atom  the structure

Particularly preferred compounds of the formula IVc are those of the Formula IVc ′:

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

The dielectrics according to the invention are produced in the usual way. As a rule, the Components dissolved in each other, useful for increased Temperature.

By means of suitable additives, the liquid crystalline Dielectrics are modified according to the invention that they are known in all types of Liquid crystal display elements can be used. Such additives are known to the expert and in the Literature described in detail. For example, you can Conductive salts, preferably ethyl-dimethyl-dodecyl-ammonium 4-hexyloxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf. e.g. I. Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973)) to improve conductivity, dichroic Dyes for the production of colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases are added. Such substances  are z. B. in DE-OS 22 09 127, 22 40 854, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 and 29 02 177 described.

The following examples are intended to illustrate the invention, without limiting it. F. = melting point, K. = clearing point. Percentages above and below mean percentages by weight percent; all temperatures are in degrees Celsius specified. "Usual work-up" means: one gives Add water, extract with methylene chloride, separate, dries the organic phase, evaporates and cleans the product by crystallization and / or chromatography.

Example 1

To a mixture of 1.78 g of 5-n-pentyl-5,6-dihydro-4-H- cyclopenta [b] thiophene-2-carboxylic acid (can be prepared from 3-Bromomethylthiophene by reaction with n-heptane carbon acid and lithium diisopropylamide, followed by ring closure about the corresponding acid chloride, reduction the carbonyl group (e.g. Wolff-Kishner reduction), Friedels Craft Acetylation and Haloform Reaction) 0.098 g of 4-dimethylaminopyridine, 1.42 g of 4-n-heptylphenol and 12 ml of dichloromethane are stirred at 10 ° 1.63 g dicyclohexylcarbodiimide in 2.5 ml dichloromethane admitted. After stirring for 15 hours at room temperature is suctioned off over silica gel and the solvent is evaporated. After recrystallization from ethanol 5-n-pentyl-5,6-dihydro-4-H-cyclopenta [b] -thiophene- 2-carboxylic acid (4-n-heptylpehnyl) ester with mp 64 ° and K. 82 °.  

The following are produced analogously:

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-n-heptylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-isopropylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butyloxyphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentyloxyphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexyloxyphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptyloxyphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-heptylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-propylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-isobutylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-pentyloxyphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-hexyloxyphenyl) ester

5-Methty-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid (4-butyloxyphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-butylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-propylphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-ethylphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-pentyloxyphenyl) ester

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester
5-Octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-hexyloxyphenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (4-heptyloxyphenyl) ester

Example 2

Analogously to Example 1, 5-n-pentyl-5,6-dihydro- 4-H-cyclopenta [b] thiophene-2-carboxylic acid by reaction with 3-fluoro-4-cyanophenol 5-n-pentyl-5,6-dihydro-4-H- cyclopenta [b] thiophene-2-carboxylic acid- (3-fluoro-4-cyano phenyl) ester with F. 49 ° and K. 93 °.

The following are produced analogously:

5-Methyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid-3-fluoro-4-cyanophenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] furan-2-carboxylic acid 3-fluoro-4-cyanophenyl) ester

5-methyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-ethyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Propyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-butyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Pentyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-Hexyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-heptyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester
5-octyl-5,6-dihydro-4-H-cyclopenta [b] pyrrole-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester

Example 3

To a mixture of 1.4 ml diisopropylamine in 10 ml THF 6.1 ml of a 15% solution of are given at -20 ° Butyllithium in hexane. Then give at -60 ° 3.3 g 2- (4-n-hexyloxyphenyl) -5-cyano-5,6-dihydro-4- H-cyclopenta [d] thiazole (can be prepared from 2- (4-n-hexyloxy phenyl) thiazole-2,3-dicarboxylic acid ethyl ester a) reduction of the carbonyl groups, b) conversion into the Tosylate, c) Ring closure by reaction with malonic acid  diethyl ester, d) saponification and decarboxylation and e) introduction of the nitrile group in 10 ml of THF, stir for 15 minutes, then add 1.8 g of 1-bromoheptane, Stir for another 30 minutes at -60 ° and leave overnight stir at room temperature. It is mixed with 10% Ammonium chloride solution, then works up as usual and obtains 2- (4-n-hexyloxyphenyl) -5-cyano-5-n-heptyl-5,6- dihydro-4-H-cyclopenta [d] thiazole.

The following are produced analogously:

2- (4-Hexyloxyphenyl) -5-cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-Hexyloxyphenyl) -5-cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-Hexyloxyphenyl) -5-cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-Hexyloxyphenyl) -5-cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-Hexyloxyphenyl) -5-cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-Hexyloxyphenyl) -5-cyano-5-octyl-5,6-dihydro-4-H-cyclopenta [d] thiazole

2- (4-pentyloxyphenyl) -5-cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-pentyloxyphenyl) -5-cyano-5-octyl-5,6-dihydro-4-H-cyclopenta [d] thiazole

2- (4-butyloxyphenyl) -5-cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-butyloxyphenyl) -5-cyano-5-octyl-5,6-dihydro-4-H-cyclopenta [d] thiazole

2- (4-heptyloxyphenyl) -5-cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-heptyloxyphenyl) -5-cyano-5-octyl-5,6-dihydro-4-H-cyclopenta [d] thiazole

2- (4-octyloxyphenyl) -5-cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [d] thiazole
2- (4-octyloxyphenyl) -5-cyano-5-octyl-5,6-dihydro-4-H-cyclopenta [d] thiazole

Example 4

To a mixture of 2.9 g of 5-cyano-5-n-heptyl-5,6- dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (her adjustable from thiophene-2,3-dicarboxylic acid ethyl ester Saponification, decarboxylation, introduction of the cyano group, Introduction of the n-heptyl group analogous to Example 3, Friedel-Crafts acetylation in the 2-position and subsequent Haloform reaction), 0.12 g of 4-dimethylamino pyridine, 2.0 g of 4-n-octylphenol and 20 ml of dichloromethane 2.1 g of dicyclohexylcarbodiimide are added at 10 ° with stirring in 5 ml dichloromethane and then stirred 15 hours at room temperature. You suck over silica gel off, the solvent evaporates and after Um crystallization from ethanol 5-cyano-5-n-heptyl-5,6- dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid- (4-n- octylphenyl) ester.  

The following are produced analogously:

5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester

5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester
5-Cyano-5-hexyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-octylphenyl) ester

5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester
5-Cyano-5-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-octylphenyl) ester

5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester
5-Cyano-5-butyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-octylphenyl) ester

5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester
5-Cyano-5-propyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-octylphenyl) ester

5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-propylphenyl) ester
5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-butylphenyl) ester
5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-pentylphenyl) ester
5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-hexylphenyl) ester
5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (4-heptylphenyl) ester
5-Cyano-5-ethyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-octylphenyl) ester

5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-octyloxyphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-heptyloxyphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-hexyloxyphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-pentyloxyphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-butyloxyphenyl) ester
5-Cyano-5-heptyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid - (4-propyloxyphenyl) ester

The following examples relate to liquid crystalline phases.

Example A

A liquid crystalline phase consisting of

12.8% 5-n-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid (3-fluoro-4-cyanophenyl) ester, 5.1% 4-ethylbenzoic acid ( 3-fluoro-4-cyanophenyl) ester, 5.1% 4-propylbenzoic acid (3-fluoro-4-cyanophenyl) ester, 7.1% p- (trans-4-propylcyclohexyl) benzoic acid (3-fluoro-4 -cyanophenyl) ester, 5.1% 2-p-pentyloxyphenyl-5-pentylpyrimidine, 5.1% 2p-hexyloxyphenyl-5-hexylpyrimidine, 7.1% trans-1-p-butyloxyphenyl-4-propylcyclohexane, 5.1 % 2-n-propylphenyl-5-propylpyrimidine, 5.1% 2-p-propylphenyl-5-pentylpyrimidine, 15.2% butyric acid (p-trans-4-propylcyclohexylphenyl ester), 14.2% trans-1- p-Propylphenyl-4-pentylcyclohexane, 4.1% 4- (trans-4-propylcyclohexyl) -4 ′ - (trans-4-propyl cyclohexyl) biphenyl, 5.1% 4- (trans-4-pentylcyclohexyl) - 4 '- (trans-4-propylcyclohexyl) biphenyl
and 4.1% 4- (trans-4-pentylcyclohexyl) -4 ′ - (trans-4-pentyl cyclohexyl) biphenyl

has a clearing point of 67 °.

Example B

A liquid crystalline phase consisting of

16% 4-ethyl-4'-cyanbiphenyl, 20% 4-butyl-4'-cyanbiphenyl, 18% 4-pentyl-4'-cyanbiphenyl, 21% trans-4-ethylcyclohexane-carboxylic acid (4-cyan biphenyl ester), 9% p-methylbenzoic acid (p-pentylphenyl ester), 11% p-propylbenzoic acid (p-pentylphenyl ester)
and 5% 5-n-pentyl-5,6-dihydro-4-H-cyclopenta [b] tiophene-2-carboxylic acid (4-n-heptylphenyl) ester

has a clearing point of 63 °.  

Example C

A liquid crystalline phase consisting of

35% 4-pentyl-4'-cyanbiphenyl, 17% 4-heptyl-4'-cyanbiphenyl, 19% p-trans-4-propylcyclohexyl-benzonitrile, 6% 4-p-cyanophenyl-4'-pentylbiphenyl, 8% 4 -Cyan-4 ′ - (trans-4-pentylcyclohexyl) biphenyl, 5% 5-n-pentyl-5,6-dihydro-4-H-cyclopenta [b] thiophene-2-carboxylic acid- (4-n-heptylphenyl) ester, 4% 4- (trans-4-propylcyclohexyl) -2-fluoro-4'- (trans-4-propylcyclohexyl) biphenyl
and 6% 4- (trans-4-pentylcyclohexyl) -2-fluoro-4'- (trans-4-propylcyclohexyl) biphenyl

has a clearing point of 80 °.

Example D

A liquid crystalline phase consisting of

9% r-1-cyano-cis-4- (trans-4-propylcyclohexyl) -1-propyl-cyclohexane, 5% 2- (4-n-hexyloxyphenyl) -5-cyano-5-n-heptyl- 5, 6-dihydro-4-h-cyclopenta [d] thiazole, 28% 1- (trans-4-propylcyclohexyl) -2- (2'-fluoro-4'-ethylbiphenyl-4-yl) ethane, 28% 1- ( trans-4-propylcyclohexyl) -2- (2'fluoro-4'-pentylbiphenyl-4-yl) ethane, 26% 1- (trans-4-pentylcyclohexyl) -2- (2'-fluoro-4'-ethylbiphenyl- 4-yl) ethane
and 4% 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′ - (trans- 4-propylcyclohexyl) biphenyl

has a clearing point of 95 °.

Example E

A liquid crystalline phase consisting of

8% r-1-cyano-cis-4- (trans-4-ethylcyclohexyl) -1-propyl-cyclohexane, 6% 5-cyano-5-n-heptyl-5,6-dihydro-4-H-cyclo penta [b] thiophene-2-carboxylic acid (4-n-octyl oxyphenyl) ester 27% 1- (trans-4-propylcyclohexyl) -2- (2'-fluoro-4'-ethylbiphenyl-4-yl) ethane, 27 % 1- (trans-4-propylcyclohexyl) -2- (2'-fluoro-4'-pentylbiphenyl-4-yl) ethane, 24% 1- (trans-4-pentylcyclohexyl) -2- (2'-fluoro- 4'-ethylbiphenyl-4-yl) ethane, 5% 4- (trans-4-propylcyclohexyl) -2-fluoro-4'- (trans-4-propylcyclohexyl) biphenyl
and 3% 4- (trans-4-pentylcyclohexyl) -2-fluoro-4'- (trans-4-propylcyclohexyl) biphenyl

has a clearing point of 93 °.

Claims (6)

1. Heterocyclic liquid crystal compounds containing the structural element A whereinM H, CN, NCS, halogen or an alkyl group with 1-5 C atoms,
X CR⁴ or N,
Y CHR⁴, O, S or NR⁵,
R⁴ H, alkyl with 1-15 C atoms, halogen or cyan and
R⁵ is H or alkyl with 1-15 C atoms, with the proviso that in the case Y = CHR⁴X means N. 2. Heterocyclic compounds of the structure wing group ring (bridge member ring) _(1-3) wing group, characterized in that at least one ring represents the structural element A, wherein X, Y and M have the meanings given in claim 1. 3. Heterocyclic compound of the formula I R¹-A¹-Z¹-A²-R² (I) whereinR¹ and R² each independently of one another an unsubstituted or substituted alkyl group having 1-15 C atoms, in which also one or more CH₂ groups by one Grouping from the group -O-, -CO-, -CH-halogen-, -CHCN-, -O-CO-, -CO-O- and -CH = CH- or can be replaced by a suitable combination of two groups , where two heteroatoms are not directly linked to one another, one of the radicals R¹ and R² also H, F, Cl, BR, -CN, -NCS or R³- (A³) _p -Z²-,
A¹ -A-, -A⁴-Z³-A- or -A-Z³-A⁴-,
A², A³ and A⁴ are each 1,4-phenylene which is unsubstituted or substituted by one or more F and / or Cl atoms and / or CH₃ groups and / or CN groups, in which also one or two CH groups are substituted by N- Atoms can be replaced, 1,4-cyclohexylene, in which one or two non-adjacent CH₂ groups can also be replaced by O atoms and / or S atoms, piperidine-1,4-diyl, 1,4-bicylo (2nd , 2,2) octylene, unsubstituted or CN-substituted decahydro naphthalene-2,6-diyl or 1,2,3,4-tetra hydronaphthalene-2,6-diyl,
Z¹, Z² and Z³ each -CO-O, O-CO-, -OCH₂-, -CH₂O-, -CH₂CH₂- substituted ethylene or a single bond,
R³ H, an unsubstituted or substituted alkyl group with 1-15 C atoms, in which also one or more CH₂ groups by a group from the group -O-, -CO-, -CH-halogen-, -CHCN-, -O -CO-, -CO-O and -CH = CH- or can be replaced by a suitable combination of two groupings, two heteroatoms not being directly linked to one another, F, Cl, Br, -NCS or -CN,
p 1 or 2 and
A the structural element is, wherein, MH, CN, NCS, halogen or an alkyl group with 1-5 C atoms,
X CR⁴ or N,
Y CHR⁴, O, S or NR⁵,
R⁴ H, alkyl with 1-15 C atoms, halogen or cyan and
R⁵ is H or alkyl with 1-15 C atoms, where the groups A³ can be the same or different for p = 2, with the proviso that in the case of Y = CHR⁴ XN. 4. Use of the compounds according to claim 1, 2 or 3 as components of liquid crystalline phases. 5. Liquid crystalline phase with at least two liquid crystalline components, characterized in that at least one component is a connection according to claim 1, 2 or 3. 6. Electro-optical display element based on a Liquid crystal cell, characterized in that it contains a phase according to claim 5.