JP3429816B2 - Chlorodifluoromethoxyphenyl derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to novel liquid crystal compounds having chlorodifluoromethoxyphenyl groups, their preparation, liquid crystal mixtures containing such compounds, and their use for optical or electro-optical purposes.

[0002]

BACKGROUND OF THE INVENTION Since the optical properties of liquid crystals can be influenced by the applied voltage, such materials are mainly used as dielectrics for display devices. Liquid crystal based electro-optical devices are well known to those skilled in the art and can be based on various effects. The most common display device has a twisted nematic structure, based on the Schatt-Helflitsch effect. Examples of such cells are TN (“twisted nematic”) cells, STN (“super twisted nematic”) cells,
Or a display device, such as a TFT (“thin film transistor”) cell, which is actively addressed.

Liquid crystal materials for such cells must have good chemical and thermal stability and good stability to electric and electromagnetic radiation. Furthermore, the liquid crystal material must possess a low viscosity and in the cell exhibit a short response time, a low threshold potential and a high contrast. At normal operating temperature,
It must have a suitable mesophase, for example the nematic or cholesteric phase for the cells mentioned above. Furthermore, the dielectric anisotropy should be as high as possible.

Since liquid crystals are usually used as a mixture of several components, it is also important that the components have good miscibility with each other.

[0005]

The goal of liquid crystal research is, inter alia, to provide components for the above applications which have as many of the described properties as possible. Here, it has been found that components having a chlorodifluoromethoxyphenyl group are particularly suitable for the above applications.

[0006]

Accordingly, the present invention provides a compound represented by the general formula (I):

[0007]

[Chemical 3]

(In the formula, A ¹ and A ² are each independently trans-1,4-cyclohexylene and trans-
1,3-dioxane-2,5-diyl, pyridine-2,
Represents 5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene which is unsubstituted or mono- or di-substituted by fluorine, cyano and / or methyl; Z
¹ and Z ² are each independently a single bond, —CH ₂ CH ₂
-, - C1,4- phenylene; Z ¹ and Z ²
They are each independently a single _{bond, -CH 2 CH 2 -, -} C
_{H 2 O -, - OCH 2} -, - C C -, - COO -, -
_{OOC -, - (CH 2)} 4 -, - O (CH 2) 3 -, -
(CH _{2) 3} O-, or trans, -CH = CH
-, - CH = CH (CH 2) 2 -, - (CH 2) 2 CH
= CH -, - CH = CHCH 2 O-, or -OCH
₂ represents CH = CH-; R is 1 to 1 carbon atom respectively.
12 or 2 to 12 alkyl or alkenyl (optionally 1 to 3 hydrogen atoms may be replaced by fluorine, and / or 1 to 2 non-adjacent CH ₂ groups may be replaced by O) And X ¹ , X ² and X ³ each independently represent hydrogen or fluorine; provided that (a) ring A ¹ is ring A ² is a (hetero) aromatic ring. Is not saturated and / or (b) two (complex)
Z ¹ and Z ² between the aromatic rings are a single covalent bond, —COO—
Or -OCC-, and / or (c) the substituent X ¹ ,
No more than two of X ² and X ³ represent fluorine).

The compounds according to the invention are liquid crystals having a relatively high clearing point and a broad, partially pure nematic mesophase. They are soluble in one another in relatively high concentrations and also with other known liquid crystals and are therefore particularly suitable as components of nematic or cholesteric mixtures. In the experimental mixture, the compounds according to the invention hardly raise, and often even even lower, the threshold potential, in spite of the desired clear rise of the clearing point and their favorable relatively small polarity. It was unexpectedly found. Moreover, the switch connection times in the corresponding mixtures are relatively short. The optical anisotropy can be varied within wide limits by appropriate choice of the ring of formula (I); for example, the rings A ¹ and A ² can be trans-1,4-cyclohexylene and / or trans-. 1,3-dioxane-2,5
The compound of the general formula (I) which represents -diyl has a low optical anisotropy, and the compound of the formula (I) in which the rings A ¹ and A ² represent an aromatic ring and / or a heteroaromatic ring has a high optical anisotropy. Have anisotropy. Therefore, such a compound can be conveniently used as a mixture for TN-LCD or STN-LCD in order to optimize the optical retardation when the display device has a given electrode spacing. The relatively low total polarities of the compounds according to the invention with the relatively high dielectric anisotropy also enable their use as components of TFT mixtures.

In the above definition of compounds of formula (I)
The term "trans-1,4-phenylene) which is unsubstituted or mono- or di-substituted by fluorine, cyano and / or methyl" is for example 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-difluoro-1,4-phenylene, 2-cyano-1,4-phenylene, 2,3-dicyano-1,4-phenylene, 2
Means groups such as -cyano-3-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene and the like.

Within the scope of the present invention, the term "(hetero) aromatic ring" means pyridine-2,5-diyl, pyrimidine-2,5-diyl and unsubstituted or fluorine, cyano and / or
Or 1,4-phenylene mono- or di-substituted by methyl, the term "saturated ring" means trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5 -Means jiile.

"1-12 carbon atoms or 2 carbon atoms, respectively
~ 12 alkyl or alkenyl (optionally 1 to 3)
Hydrogen atoms may be replaced by fluorine, and /
Or 1-2 non-adjacent CH ₂ groups may be replaced by O) ”refers to straight-chain and branched (optionally chiral) residues such as alkyl, 1E-alkenyl, 3E-alkenyl. , 4-alkenyl, alkenyl having a terminal double bond, alkoxy, alkoxyalkyl, 2E-alkenyloxy, 3-alkenyloxy,
Alkenyloxy having a terminal double bond, alkenyloxyalkyl, alkoxyalkenyl, 1-fluoroalkyl, 1,1-difluoroalkyl, 2-fluoroalkyl, 2-fluoroalkoxy, terminal fluoroalkyl, terminal difluoromethylalkyl, terminal trifluoro. Methylalkyl, terminal trifluoromethylalkoxy,
1-methylalkyl, 2-methylalkyl, 1-methylalkoxy, 2-methylalkoxy and the like are included. Examples of preferred residues are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 1-methylpropyl, 1-methylheptyl, 2-methylbutyl, 3-methylpentyl, vinyl, 1E-propenyl,
1E-butenyl, 1E-pentenyl, 1E-hexenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 4-pentenyl, 4Z-hexenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, methoxy, ethoxy, propyloxy , Butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 1-methylpropyloxy, 1-methylheptyloxy, 2-methylbutyloxy, allyloxy, 2E-
Butenyloxy, 2E-pentenyloxy, 3-butenyloxy, 3Z-pentenyloxy, 4-pentenyloxy, 5-hexenyloxy, 6-heptenyloxy,
7-octenyloxy, 2-methoxyethyl, 3-methoxypropyl, 1E-3-methoxypropenyl, 1-fluoropropyl, 1-fluoropentyl, 2-fluoropropyl, 2,2-difluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-
Trifluoropropyl, 2-fluoropropyloxy,
3-fluoropropyloxy, 2,2-difluorovinyl, 2- (3,3-difluoro) propenyl and the like.

Preferred compounds of formula (I) are of general formula (I
a) to (Ik):

[0014]

[Chemical 4]

[Wherein, X ¹ , X ² , X ³ , Z ¹ , Z ² and R have the above meanings].

Preferred compounds of formulas (I) and (Ia) to (Ik) are those in which one of the groups Z ¹ and Z ² is a single bond or --C≡.
Represents C-, and the other of the groups Z ¹ and Z ² is a single bond,
_{CH 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - C≡
It is a compound that also represents C—, —COO—, OOC— or trans type —CH═CH— between two non-aromatic rings.
However, particularly preferred are one of the radicals Z ¹ and Z ² represents a single bond, and the other is a single bond groups Z ¹ and Z ^2, -CH ₂ CH ₂ - in compounds representative of the or -C≡C- is there.

Preferably, the above formulas (I) and (Ia)
The residues R in (Ik) are each 1 to
It has a chain length of 7 or 2 to 7. Residues having 2 to 5 carbon atoms are particularly preferred.

Either X ¹ , X ² or X ³ represents hydrogen, X ² represents fluorine and the other two substituents represent hydrogen, or X ¹ and X ² represent fluorine. , And X ³ represents hydrogen, or X ¹ represents hydrogen and the other two substituents represent fluorine, are also suitable. However, a compound of formula (I) in which X ¹ , X ² and X ³ represent hydrogen, or X ² represents fluorine,
And compounds of formula (I) in which the other two substituents represent hydrogen are particularly preferred.

The compounds of formula (I) can be prepared by reaction sequences known per se, starting from chlorodifluoromethoxybenzene derivatives which are suitably functionalized in the para position. The synthesis of such a chlorodifluoromethoxybenzene derivative is shown in Scheme 1. The starting materials for these syntheses are known compounds or analogs of known compounds. Moreover, many of them are commercially available.

[0020]

[Chemical 5]

In the above formula, X ¹ , X ² and X ³ have the meanings given above.

For example, p-bromo derivatives of the general formula (II) are prepared by reacting optionally fluoro-substituted phenols with the corresponding difluoromethoxy compounds by reaction with chlorodifluoromethane in a strong base. , Can be manufactured. It can then be converted to the corresponding chlorodifluoromethoxy derivative by photochlorination and then to the compound (II) by subsequent iron (III) catalyzed bromination. Similarly,
P-difluoromethoxybenzoic acid, known from the literature,
Alternatively, one of its fluorinated analogues (III) can be converted beforehand to the acid chloride and then directly converted to the corresponding chlorodifluoromethoxybenzoyl chloride (IV) by chlorination. If desired, stoichiometric amounts of zinc (II) chloride and palladium-1,1′-bis (diphenylphosphino) ferrocene (PdCl ₂ [dpp
Acetophenone derivatives or compounds of formula (IVb) can be prepared therefrom by reaction with a methyl Grignard reagent using f]) as a catalyst. Formula (IVd)
The above phenols can be prepared from (IVb) by Baeyer-Villiger oxidation followed by saponification with alkali. The corresponding nitrites of formula (IVa) are also prepared starting from the optionally fluoro-substituted p-cyanophenol by a reaction sequence similar to that for the compounds of formula (II) (eliminating the bromination step). be able to. The aldehyde of formula (IVc) is the corresponding acid chloride (II
It can be prepared either by Rosenmund reduction of I) or DIBAH reduction of the corresponding nitrile (IVa).

The compounds of formula (I) start from intermediates (II), (IV) and (IVa) to (IVd) described above,
It can be prepared by a reaction sequence usually used in LC chemistry. Such reaction sequences are well known to those skilled in the art and are extensively described in the literature. Essential reaction partners are known from the literature or are analogues of known compounds and can be prepared by known methods. For example, a compound of formula (I) in which A ¹ represents 1,4-phenylene or 1,4-cyclohexylene and Z ¹ represents a single bond or an acetylene bridge is prepared by the coupling reaction shown in Scheme 2 (II) Can be prepared from an intermediate of the type

[0024]

[Chemical 6]

In the above formula, R ¹ , A ¹ , A ² , Z ¹ , Z
² , X ¹ , X ² and X ³ have the meanings given above.

Compounds of formula (I) in which ring A ¹ represents 1,3-dioxane-2,5-diyl and Z ¹ represents a single bond are
It is conveniently prepared by acetal formation of the appropriate diol with an aldehyde of formula (IVc). Compounds of general formula (I) in which Z ¹ represents a 1,2-ethylene bridge can also be prepared from the same aldehyde by the Wittig reaction with a suitable Wittig salt followed by catalytic hydrogenation. Compounds of formula (I) in which ring A ¹ represents pyrimidine-2,5-diyl can be prepared from a nitrile of formula (IVa) via the corresponding amidinium salt or an aldehyde (IVc)
Is conveniently synthesized after converting the aldehyde group to a malonyl tetraacetal group. Ring A ¹ is pyridine-
Acetophenone derivatives (IVb) as starting materials for the corresponding compounds of general formula (I) representing 2,5-diyl
Can be reacted in a known order starting from the Mannich reaction. General formula (I) in which Z ¹ represents a methyleneoxy group
The compounds of (1) can be obtained by the alkaline etherification of phenol (IVd) with appropriately substituted methylene halides. Esters of formula (I) in which Z ¹ represents a carboxyl group can be prepared by esterifying the acid chloride with a suitable alcohol or the phenol (IVd) with the corresponding acid chloride.

The compounds of formula (I) are mixed with one another and / or
Alternatively, it can be used in the form of a mixture with other liquid crystal components. Suitable liquid crystal components are known to those skilled in the art, for example D. Demus.
Et al: "Fluessige Kristalle in Tabellen," Volumes 1 and 2 (VEB Deutscher Verlagfuer Grundstoffindustr
, Leipzig), and many of them are commercially available as well.

The invention therefore also relates to a liquid crystal mixture having at least two components, at least one of which is a compound of formula (I).

In view of the good solubility of the compounds of the general formula (I) in other liquid crystal materials and their good miscibility with one another, the inclusion of the compounds of the formula (I) in the mixtures according to the invention. The amount may be relatively high, for example 1 to 70% by weight. Generally, about 3 to 4 compounds of formula (I)
A content of 0% by weight, especially about 5 to 30% by weight, is preferred.

The mixtures according to the invention, in addition to one or more compounds of the general formula (I), preferably have the general formulas (IX) to
It contains one or more compounds from the group of compounds represented by (XXVII).

[0031]

[Chemical 7]

[0032]

[Chemical 8]

In the above formula, R ¹ and R ⁴ also represent alkyl, alkoxyalkyl, 3E-alkenyl, 4-alkenyl or 1E-alkenyl in the saturated ring; n is 0.
Or 1 is represented; ring A ³ is 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene or trans-1,3
Represents dioxane-2,5-diyl; R ² is cyano,
Represents isothiocyanato, fluorine, alkyl, 3E-alkenyl, 4-alkenyl, alkoxy, 2E-alkenyloxy, 3-alkenyloxy or 1-alkynyl; ring A ⁴ is 1,4-phenylene or trans-1,4.
Represents cyclohexylene; R ³ is alkyl, 3E-alkenyl, 4-alkenyl, 1E-alkenyl in trans-1,4-cyclohexylene, or 1,4-
In phenylene, it represents cyano, isothiocyanato, alkoxy, 2E-alkenyloxy or 3-alkenyloxy; R ⁵ is alkyl, 1E-alkenyl,
Represents 3E-alkenyl or 4-alkenyl; R ⁶ represents cyano, alkyl, 1E-alkenyl, 3E-alkenyl, 4-alkenyl, alkoxy, 2E-alkenyloxy, 3-alkenyloxy, alkoxymethyl or (2E-alkenyl) oxy. Represents methyl; Z ³ and Z
⁴ is a covalent single bond, or a -CH ₂ CH ₂ - represents a proviso two aromatic rings are always covalently bond; R ⁷
Represents hydrogen, fluorine or chlorine; R ⁸ represents cyano, fluorine or chlorine; R ⁹ represents hydrogen or fluorine; and R ¹⁰ represents fluorine or chlorine.

The term "aromatic ring" above refers in this connection to, for example, 1,4-phenylene, pyridine-
By a ring such as 2,5-diyl or pyrimidine-2,5-diyl is meant. The term "saturated ring" means trans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl.

The residues R ¹ to R ⁶ each preferably have 1 to 12, especially 1 to 7 carbon atoms. Linear residues are generally preferred. The term "alkyl" in this connection preferably refers to 1 to 12 carbon atoms.
And especially 1 to 7 carbon atoms are meant residues such as methyl, ethyl, propyl, butyl, hexyl or heptyl.

The term "alkyloxyalkyl" in this connection means a residue which is preferably straight-chain, such as methoxymethyl, ethoxymethyl, propyloxymethyl, butyloxymethyl and the like.

The term "alkyloxy" means in this connection preferably linear residues such as methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy and the like.

The term "1E-alkenyl" is in this connection preferably a linear alkenyl residue in which the double bond is located in the 1-position, for example vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E. -Hexenyl, 1E-heptenyl and the like.

The term "3E-alkenyl" is in this connection preferably a straight-chain alkenyl residue in which the double bond is located in the 3-position, for example 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl. And so on.

The term "4-alkenyl" is in this connection preferably a straight-chain alkenyl residue in which the double bond is located in the 3-position, for example 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl. And so on.

The term "4-alkenyl" in this context means a straight-chain alkenyl residue, preferably in which the double bond is located in the 4-position, such as 4-pentenyl, 4-hexenyl, 4-heptenyl and the like. .

The term "2E- or 3Z-alkenyloxy" is in this connection a straight-chain alkenyloxy, preferably in which the double bond is located in the 2 or 3 position and E or Z represents the preferred configuration. Residues such as allyloxy, 2E-butenyloxy, 2E-pentenyloxy, 2E-hexenyloxy, 2E-heptenyloxy, 3-butenyloxy, 3Z-pentenyloxy, 3
Z-hexenyloxy, 3Z-heptenyloxy, 4-
It means pentenyloxy, 5-hexenyloxy, 6-heptenyloxy and the like.

The term "1-alkynyl" in this connection is preferably a straight-chain alkynyl residue in which the triple bond is located in position 1, eg ethynyl, 1-propynyl,
It means 1-butynyl, 1-pentynyl and the like.

The mixtures according to the invention comprise optically active compounds (for example optically active 4'-alkyl- or 4 '.
-Alkoxy-4-biphenylcarbonitrile) and /
Alternatively, it may contain a coloring substance (for example, an azo, azoxy or anthraquinone coloring substance). The content of such compounds is determined by the solubility, desired pitch, color, absorbance, etc. In general, the content of optically active compound and coloring substance is in each case up to about 10% by weight in the final mixture.

The production of the liquid crystal mixture and the production of the electro-optical device according to the invention can be carried out in a manner known per se.

[0046]

EXAMPLES The following examples further illustrate the preparation of compounds of formula (I) and liquid crystal mixtures containing these compounds. C means crystalline phase, S means smectic phase, N means nematic phase and I means isotropic phase. V ₁₀ means the voltage for 10% transmission (perspective angle is perpendicular to the plate surface). t _on and t
_off means switch connection time and switch cutoff time, respectively, and Δ _n means optical anisotropy.

Example 1 (a) 39.2 g of o-fluorophenol, 200 ml of isopropanol and 20% 25% sodium hydroxide solution.
Chlorodifluoromethane was introduced into 0 ml of the mixture at 70 ° C. for 9 hours at a rate of about 1 bubble / second. During this time, an additional 20 ml of 25% sodium hydroxide solution was added so that the reaction solution was always basic. Then the reaction mixture was cooled and left at room temperature for several hours. The liquid phase was then transferred to a separatory funnel and the upper organic phase was separated. The precipitate remaining in the reactor was washed several times with ether and the ether phase was combined with the organic phase. It was then washed with 5% sodium hydroxide solution, then with alkali-free water, dried over magnesium sulphate, filtered and the solvent was evaporated. Distill the residue under reduced pressure (69-71 ℃, 55mmHg)
And 2-fluoro-difluoromethoxybenzene 29 g
Got

(B) 2-fluorodifluoromethoxybenzene dissolved in 300 ml of dry carbon tetrachloride.
3 g was introduced into a quartz vessel having a gas inlet, a reflux condenser and an attached gas dryer containing sulfuric acid. Reflux and U
Chlorine gas was introduced for 25 hours under V irradiation (quartz mercury lamp). Then the mixture was cooled, the solvent was evaporated and the residue was fractionated under reduced pressure (83-85 ° C, 80 mmHg).
This gave 16.2 g of 2-fluoro-chlorodifluoromethoxybenzene. n _D ^20: 1.4730.

(C) To a mixture of 9.8 g of 2-fluoro-chlorodifluoromethoxybenzene, 40 ml of anhydrous carbon tetrachloride and 1.5 g of iron trichloride was added dropwise 8.1 g of bromine within 30 minutes at 30 to 35 ° C. . The solution is cooled immediately when the release of hydrogen bromide gas can no longer be measured,
It was filtered, washed first with water, then with 5% sodium bisulfite solution and again with water and dried over magnesium sulphate. Distillation of solvent and fractional distillation (81-83 ℃, 15mm
Hg) gave 8.8 g of 2-fluoro-4-bromo-chlorodifluoromethoxybenzene. n _D ²⁰ : 1.
4858.

The following compounds could be prepared in an analogous manner:

4-Bromo-chlorodifluoromethoxybenzene, boiling point: 67 to 68 ° C. (11 mmHg), n _D ²⁰ :
1.4815, 2,3-difluoro-4-bromo-chlorodifluoromethoxybenzene, 2,6-difluoro-
4-Bromo-chlorodifluoromethoxybenzene.

Example 2 (a) A mixture of 23.8 g of 4-hydroxybenzonitrile dissolved in 400 ml of dioxane and a solution of 60 g of sodium hydroxide dissolved in 300 ml of water was stirred at 40 ° C. with chlorodifluoromethane. Methane was introduced at a rate of about 1 bubble / second for 7 hours. In doing so, care was taken that the temperature did not exceed 45 ° C. Operating as in Example 1 (without distillation) and after precipitation from pentane, 4
-Difluoromethoxybenzonitrile (melting point: 41-4
(2 ° C.) 23 g was obtained.

(B) While introducing chlorine gas into the apparatus described in Example 1 (b), 150 ml of anhydrous carbon tetrachloride was added with 4-gas.
A solution in which 6.76 g of difluoromethoxybenzonitrile was dissolved was irradiated at reflux temperature for 4.5 hours. After completion of the reaction, the solvent was evaporated and the residue was fractionated under reduced pressure (115
~ 117 ° C, 22 mmHg). This gave 5.85 g of 4-chlorodifluoromethoxybenzonitrile. n
_D ^20: 1.4855.

The following compounds could be prepared in an analogous manner:

2-Fluoro-4-chlorodifluoromethoxybenzonitrile, 2,3-difluoro-4-chlorodifluoromethoxybenzonitrile, 2,6-difluoro-4-chlorodifluoromethoxybenzonitrile.

Example 3 (a) 4-difluoromethoxybenzoic acid [manufactured by J.
A. Fialkov et al .: Ukr. Khim. J., 49, 181 (1983), CA98.
(23) According to 197713n] 18.8 g and phosphorus pentachloride 21 g
The mixture was heated to 130 ° C. Gently shake the reaction mixture at 130 ° C until no hydrogen chloride gas is released.
Kept at. Then, the mixture was cooled, the phosphorus oxychloride formed was evaporated, and the residue was fractionated under reduced pressure (112-
114 ° C, 12 mmHg). 19.6 g of 4-difluoromethoxybenzoyl chloride was obtained.

(B) In the same manner as in Example 1, 400 ml of anhydrous carbon tetrachloride was added to 4-difluoromethoxybenzoyl chloride 2.
Chlorine gas was introduced into the solution in which 0.65 g was dissolved for 18 hours under reflux and UV irradiation. Then cool the mixture,
The solvent was evaporated and the residue was fractionated under reduced pressure (101-1
03 ° C, 13 mmHg). 20.3 g of 4-chlorodifluoromethoxybenzoyl chloride was obtained. Melting point of amide prepared with ammonia: 145 ° C.

The following compounds could be prepared in an analogous manner:

2-Fluoro-4-chlorodifluoromethoxybenzoyl chloride, 2,3-difluoro-4-chlorodifluoromethoxybenzoyl chloride, 2,6-difluoro-4-chlorodifluoromethoxybenzoyl chloride.

Example 4 To a mixture of 25 ml of dry tetrahydrofuran and 1.25 g of magnesium cuttings was slowly added 12.8 g of 4- (4-trans-propylcyclohexyl) bromobenzene dropwise, and the mixture was refluxed at 1 g. Held for hours. The reaction mixture was then cooled to 0 ° C. and PdCl ₂ (dpp
f) 0.9 g of catalyst was added, and a solution of 13.8 g of 4-bromo-chlorodifluoromethoxybenzene was added dropwise at 0 ° C. After 30 minutes of addition, the reaction mixture was heated to reflux for 1 hour, then cooled to room temperature and treated with saturated ammonium chloride solution. The reaction solution was extracted several times with benzene, the combined organic phases were dried over magnesium sulphate, filtered and the solvent was evaporated. By chromatography on silica gel with hexane and crystallization from alcohol, 4-
6.6 g of chlorodifluoromethoxy-4 '-(4-trans-propylcyclohexyl) biphenyl was obtained. Melting point (C-S): 96 ° C, melting point (S-N): 112.5
C, clearing point (N-I): 123C.

The following compounds could be prepared in an analogous manner:

4-chlorodifluoromethoxy-4'-
(4-trans-ethylcyclohexyl) biphenyl,
4-chlorodifluoromethoxy-4 '-(4-trans-butylcyclohexyl) biphenyl, 4-chlorodifluoromethoxy-4'-(4-trans-pentylcyclohexyl) biphenyl, 4-chlorodifluoromethoxy-4 '-(4- Trans-vinylcyclohexyl) biphenyl, 4-chlorodifluoromethoxy-4 '-[4
-Trans- (1E-propenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[4
-Trans- (1E-butenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[4-
Trans- (1E-pentenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 ′-[4-
Trans- (3-butenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[4-trans- (3E-pentenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4'-[4-trans- (4 -Pentenyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[4-trans- (3-methoxypropyl) cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4'-(5-
Trans-propyl-1,3-dioxan-2-yl)
Biphenyl, 4-chlorodifluoromethoxy-4'-
(5-trans-pentyl-1,3-dioxane-2-
Yl) biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′-(4-trans-ethylcyclohexyl) biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′-(4-trans-propylcyclohexyl) biphenyl, Melting point (CN): 43 ° C, clearing point (NI): 75 ° C, 3-fluoro-4-chlorodifluoromethoxy-4 '-(4-trans-butylcyclohexyl) biphenyl, 3-fluoro-4-. Chlorodifluoromethoxy-4 '-(4-trans-pentylcyclohexyl) biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4'-(4-trans-hexylcyclohexyl) biphenyl, 3-fluoro-4-chlorodifluoromethoxy- 4 '-(4-trans-vinylcyclohexyl) biphenyl, -Fluoro-4-chlorodifluoromethoxy-4 '-[4-trans- (1E-propenyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4'-[4-trans- (1E-butenyl) cyclohexyl ] Biphenyl,
3-fluoro-4-chlorodifluoromethoxy-4'-
[4-trans- (1E-pentenyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′-[4-trans- (1E-hexenyl) cyclohexyl] biphenyl, 3-fluoro-4-
Chlorodifluoromethoxy-4 '-[4-trans-
(3-Butenyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′-[4-
Trans- (3E-Pentenyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′-[4-trans- (4-pentenyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 ′ -[4-trans- (3-methoxypropyl) cyclohexyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 '-(5-trans-propyl-1,3-dioxan-2-yl) biphenyl, 3- Fluoro-4-chlorodifluoromethoxy-
4 '-[5-trans- (1E-propenyl) -1,3
-Dioxan-2-yl] biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4 '-(4-trans-propylcyclohexyl) biphenyl, 2,3
-Difluoro-4-chlorodifluoromethoxy-4'-
(4-trans-butylcyclohexyl) biphenyl,
2,3-difluoro-4-chlorodifluoromethoxy-
4 '-(4-trans-pentylcyclohexyl) biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4'-(4-trans-vinylcyclohexyl) biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy- 4 '-[4-trans- (1E-propenyl) cyclohexyl] biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4'-[4-trans- (1E-butenyl) cyclohexyl] biphenyl, 2,3- Difluoro-4-chlorodifluoromethoxy-4 ′-[4-trans- (1E-pentenyl) cyclohexyl] biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4 ′-[4-trans- (3
-Butenyl) cyclohexyl] biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4 '-[4
-Trans- (3E-pentenyl) cyclohexyl] biphenyl, 2,3-difluoro-4-chlorodifluoromethoxy-4 '-[4-trans- (4-pentenyl)
Cyclohexyl] biphenyl, 2,6-difluoro-4
-Chlorodifluoromethoxy-4 '-(4-trans-
Propylcyclohexyl) biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4 ′-(4-trans-butylcyclohexyl) biphenyl, 2,6-
Difluoro-4-chlorodifluoromethoxy-4'-
(4-trans-Pentylcyclohexyl) biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4 '-(4-trans-vinylcyclohexyl) biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4'- [4-trans- (1E-propenyl) cyclohexyl] biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4 ′-[4-trans- (1E-butenyl) cyclohexyl] biphenyl,
2,6-difluoro-4-chlorodifluoromethoxy-
4 '-[4-trans- (1E-pentenyl) cyclohexyl] biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4'-[4-trans- (3-butenyl) cyclohexyl] biphenyl, 2,6- Difluoro-4-chlorodifluoromethoxy-4 '-[4-trans- (3E-pentenyl) cyclohexyl] biphenyl, 2,6-difluoro-4-chlorodifluoromethoxy-4'-[4-trans- (4-pentenyl) Cyclohexyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[2- (4-trans-propylcyclohexyl) ethyl] biphenyl, 4-chlorodifluoromethoxy-4'-[2- (4-trans-butylcyclohexyl) ethyl] Biphenyl, 4-chlorodifluoromethoxy-4 '-[2- (4-to Lance-pentylcyclohexyl) ethyl] biphenyl, 4-chlorodifluoromethoxy-4 '-[2- (4-trans-vinylcyclohexyl) ethyl] biphenyl, 4-chlorodifluoromethoxy-4'-[2- (4-trans- (1E-propenyl) cyclohexyl) ethyl] biphenyl, 4-chlorodifluoromethoxy-4 ′-[2- (4-trans-
(3-butenyl) cyclohexyl) ethyl] biphenyl, 4-chlorodifluoromethoxy-4 ′-[2- (5
-Trans- (3-butenyl) -1,3-dioxane-
2-yl) ethyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 '-[2- (4-trans-propylcyclohexyl) ethyl] biphenyl, 3-
Fluoro-4-chlorodifluoromethoxy-4 ′-[2
-(4-trans-Butylcyclohexyl) ethyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 '-[2- (4-trans-pentylcyclohexyl) ethyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy -4 '-[2- (4-trans-vinylcyclohexyl) ethyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4'-[2- (4
-Trans- (1E-propenyl) cyclohexyl) ethyl] biphenyl, 3-fluoro-4-chlorodifluoromethoxy-4 '-[2- (4-trans- (3-butenyl) cyclohexyl) ethyl] biphenyl, 3-fluoro- 4-chlorodifluoromethoxy-4 '-[2-
(5-trans-propyl-1,3-dioxane-2-
Iyl) ethyl] biphenyl, 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, melting point (CN): 82 ° C, clearing point (NI): 133 ℃, 1
-[Trans-4- (trans-4-butylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 1- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 1 -[Trans-4-
(Trans-4-hexylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 1-
[Trans-4- (trans-4-vinylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (1
E-Propenyl) cyclohexyl] cyclohexyl}-
4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (3-butenyl) cyclohexyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4-
(4-Pentenyl) cyclohexyl] cyclohexyl}
-4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (3-methoxypropyl)
Cyclohexyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-5- (1E-propenyl) -1,3-dioxane-
2-yl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- [trans-4- (trans-4
-Propylcyclohexyl) cyclohexyl] -3-fluoro-4-chlorodifluoromethoxybenzene, 1-
[Trans-4- (trans-4-butylcyclohexyl) cyclohexyl] -3-fluoro-4-chlorodifluoromethoxybenzene, 1- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl]
-3-Fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (1E-propenyl) cyclohexyl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1-
{Trans-4- [trans-4- (3-butenyl) cyclohexyl] cyclohexyl} -3-fluoro-4-
Chlorodifluoromethoxybenzene, 1- {trans-
4- [trans-4- (4-pentenyl) cyclohexyl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (3-methoxypropyl) cyclohexyl]
Cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-5-propyl-1,3-dioxan-2-yl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxy Benzene, 1- {trans-4- [trans-5
-(1E-propenyl) -1,3-dioxan-2-yl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2-
(Trans-4-propylcyclohexyl) ethyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-4-butylcyclohexyl) ethyl] cyclohexyl] -4-chlorodifluoromethoxybenzene, 1- {trans-4
-[2- (trans-4-pentylcyclohexyl) ethyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-
4-vinylcyclohexyl) ethyl] cyclohexyl]
-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- [trans-4- (1E-propenyl) cyclohexyl] ethyl] cyclohexyl} -4-
Chlorodifluoromethoxybenzene, 1- {trans-
4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [2-
[Trans-4- (3-methoxypropyl) cyclohexyl] ethyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-5-propyl-1,3-dioxane-2- Yl) ethyl] cyclohexyl} -4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {Trans-4- [2- (trans-
4-butylcyclohexyl) ethyl] cyclohexyl}
-3-Fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-4-pentylcyclohexyl) ethyl] cyclohexyl} -3-
Fluoro-4-chlorodifluoromethoxybenzene, 1
-{Trans-4- [2- (trans-4-vinylcyclohexyl) ethyl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- [trans-4- (1E -Propenyl) cyclohexyl] ethyl] cyclohexyl} -3-
Fluoro-4-chlorodifluoromethoxybenzene, 1
-{Trans-4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] cyclohexyl} -3
-Fluoro-4-chlorodifluoromethoxybenzene,
1- {trans-4- [2- [trans-4- (4-pentenyl) cyclohexyl] ethyl] cyclohexyl}
-3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- [trans-4- (3
-Methoxypropyl) cyclohexyl] ethyl] cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [2- (trans-5-propyl-1,3-dioxan-2-yl) ethyl ] Cyclohexyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {2- [trans-4-
(Trans-4-propylcyclohexyl) cyclohexyl] ethyl} -4-chlorodifluoromethoxybenzene, 1- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} -4-chlorodifluoromethoxybenzene, 1- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} -4-chlorodifluoromethoxybenzene, 1- {2- [trans-4- (trans-
4-vinylcyclohexyl) cyclohexyl] ethyl}
-4-chlorodifluoromethoxybenzene, 1- {2-
[Trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} -3-fluoro-4-
Chlorodifluoromethoxybenzene, 1- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {2- [trans-4
-(Trans-4-vinylcyclohexyl) cyclohexyl] ethyl} -3-fluoro-4-chlorodifluoromethoxybenzene, 1- {2- [trans-4- (trans-5-propyl-1,3-dioxane-2- Ill)
Cyclohexyl] ethyl} -3-fluoro-4-chlorodifluoromethoxybenzene.

Example 5 0.03 mol of 1-acrylyl-4-chlorodifluoromethoxybenzene [C. Botteghi et al .: Synth. Commun.,
9, 69 (1979) prepared from 4-chlorodifluoromethoxybenzaldehyde] 0.03 mol and 1-
0.03 mol of [2- (trans-4-propylcyclohexyl) vinyl] piperidine was mixed at 0 ° C, and the mixture was kept at room temperature for 2 hours. The mixture is then ethanol 9
The mixture was treated with 0 ml, water (10 ml), hydroxylamine hydrochloride (0.14 mol) and concentrated hydrochloric acid (1 ml), and heated under reflux for 8 hours. Subsequently, about 2/3 of the solvent was distilled off by distillation. The concentrated mixture was diluted with 150 ml of water and adjusted to pH 8 with aqueous sodium carbonate solution. The organic layer was extracted with benzene and the extract was washed with water until neutral, dried over magnesium sulfate, filtered and concentrated. The residue was purified by chromatography on silica gel with benzene / hexane (volume ratio 1: 1) to give 2- (4-chlorodifluoromethoxyphenyl) -5- (trans-4-propylcyclohexyl) pyridine. .

The following compounds could be prepared in an analogous manner:

2- (4-chlorodifluoromethoxyphenyl) -5- (trans-4-ethylcyclohexyl)
Pyridine, 2- (4-chlorodifluoromethoxyphenyl) -5- (trans-4-butylcyclohexyl) pyridine, melting point (C-S): 78 ° C, (S-N): 12
0.7 ° C., clearing point (SI): 129.5 ° C., 2- (4
-Chlorodifluoromethoxyphenyl) -5- (trans-4-pentylcyclohexyl) pyridine, 2- (4
-Chlorodifluoromethoxyphenyl) -5- (trans-4-vinylcyclohexyl) pyridine, 2- (3-
Fluoro-4-chlorodifluoromethoxyphenyl)-
5- (trans-4-ethylcyclohexyl) pyridine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-propylcyclohexyl) pyridine, 2- (3-fluoro-4-chlorodifluoro) Methoxyphenyl) -5- (trans-4-butylcyclohexyl) pyridine, 2- (3-fluoro-
4-chlorodifluoromethoxyphenyl) -5- (trans-4-pentylcyclohexyl) pyridine, 2-
(3-Fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-vinylcyclohexyl) pyridine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- [trans-4- (1E- Propenyl) cyclohexyl] pyridine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5-
[Trans-4- (1E-pentenyl) cyclohexyl] pyridine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- [trans-4- (3-
Butenyl) cyclohexyl] pyridine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5-
[Trans-4- (4-pentenyl) cyclohexyl]
Pyridine, 2- (3,5-difluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-propylcyclohexyl) pyridine, 2- (2,3-difluoro-4-chlorodifluoromethoxyphenyl) -5-
(Trans-4-propylcyclohexyl) pyridine,
2- (4-chlorodifluoromethoxyphenyl) -5-
[2- (trans-4-propylcyclohexyl) ethyl] pyridine, 2- (4-chlorodifluoromethoxyphenyl) -5- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine.

Example 6 A solution of 1.85 g of sodium in 30 ml of methanol was added to 0.43 mol of 3-ethoxy-2- (trans-4-propylcyclohexyl) acrolein and 4-hydrochloric acid.
Chlorodifluoromethoxybenzamidine [A. Boller
Et al., Prepared similarly to Z. Naturforsch., 33b, 433 (1978)] 0.54 mol was added dropwise at room temperature to a solution of 150 ml of methanol. The reaction mixture was stirred at room temperature for 15 hours, then adjusted to pH 4 with 25% hydrochloric acid and concentrated on a rotary evaporator. The residual mixture was diluted with water, extracted with benzene and the combined benzene extracts washed with water. Then they were dried over magnesium sulphate, filtered and the solvent was evaporated. Chromatography on silica gel with a mixture of ethyl acetate in residual toluene gave 2- (4-chlorodifluoromethoxyphenyl).
-5- (trans-4-propylcyclohexyl) pyrimidine was obtained.

The following compounds could be prepared in an analogous manner:

2- (4-chlorodifluoromethoxyphenyl) -5- (trans-4-ethylcyclohexyl)
Pyrimidine, 2- (4-chlorodifluoromethoxyphenyl) -5- (trans-4-butylcyclohexyl)
Pyrimidine, melting point (C-S): 30 ° C, same (S-N):
130.6 ° C, clearing point (N-I): 135.2 ° C, 2-
(4-chlorodifluoromethoxyphenyl) -5- (trans-4-pentylcyclohexyl) pyrimidine, 2
-(4-chlorodifluoromethoxyphenyl) -5-
(Trans-4-vinylcyclohexyl) pyrimidine,
2- (3-Fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-ethylcyclohexyl) pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-propyl Cyclohexyl) pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-butylcyclohexyl) pyrimidine, 2-
(3-Fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-pentylcyclohexyl)
Pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-vinylcyclohexyl) pyrimidine, 2- (3-fluoro-4-)
Chlorodifluoromethoxyphenyl) -5- [trans-4- (1E-propenyl) cyclohexyl] pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- [trans-4- (1E-pentenyl) cyclohexyl ] Pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- [trans-4- (3-butenyl) cyclohexyl] pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5 -[Trans-4- (4-pentenyl) cyclohexyl] pyrimidine, 2- (3,5-difluoro-4-chlorodifluoromethoxyphenyl) -5
-(Trans-4-propylcyclohexyl) pyrimidine, 2- (2,3-difluoro-4-chlorodifluoromethoxyphenyl) -5- (trans-4-propylcyclohexyl) pyrimidine, 2- (4-chlorodifluoromethoxyphenyl) -5- [2- (trans-4-propylcyclohexyl) ethyl] pyrimidine, 2- (4
-Chlorodifluoromethoxyphenyl) -5- [2-
(Trans-4-pentylcyclohexyl) ethyl] pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (4-propylphenyl) pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) ) -5- (4-Butylphenyl) pyrimidine, 2- (3-fluoro-4-chlorodifluoromethoxyphenyl) -5- (4-pentylphenyl) pyrimidine.

Example 7 A mixture of 0.05 mol of 4-chlorodifluoromethoxyphenol, 0.05 mol of trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl tosylate, 15 g of potassium carbonate and 250 ml of butanone for 2 days. Heated under reflux. Subsequently, the reaction mixture was cooled, poured into water and extracted with methylene chloride. The combined organic phases were washed with water, dried over magnesium sulphate, filtered and subsequently concentrated. Chromatography of the residue on silica gel with ethyl acetate dissolved in hexane gave 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] methoxy-4-chlorodifluoromethoxybenzene.

The following compounds could be prepared in an analogous manner:

1- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] methoxy-4-
Chlorodifluoromethoxybenzene, 1- [trans-
4- (trans-4-pentylcyclohexyl) cyclohexyl] methoxy-4-chlorodifluoromethoxybenzene, melting point (CN): 82 ° C, clearing point (NI):
133 ° C., 1- {trans-4- [trans-4- (1
E-propenyl) cyclohexyl] cyclohexyl} methoxy-4-chlorodifluoromethoxybenzene, 1-
[Trans-4- (trans-4-butylcyclohexyl) cyclohexyl] methoxy-3-fluoro-4-chlorodifluoromethoxybenzene, 1- [trans-4
-(Trans-4-pentylcyclohexyl) cyclohexyl] methoxy-3-fluoro-4-chlorodifluoromethoxybenzene, 1- {trans-4- [trans-4- (1E-propenyl) cyclohexyl] cyclohexyl} methoxy-3-fluoro -4-chlorodifluoromethoxybenzene.

Example 8 A solution of 2.6 g of 4-chlorodifluoromethoxybenzoyl chloride in 5 ml of pyridine was treated with 2.3 g of trans-4- (trans-4-propylcyclohexyl) cyclohexanol and the mixture was stirred at room temperature for 12 hours. Stir for hours. Then, the reaction mixture was poured into ice cold water and extracted with diethyl ether. The organic phase was extracted successively with 10% hydrochloric acid, saturated sodium bicarbonate solution and water, then dried over magnesium sulphate, filtered and concentrated. Ethyl acetate/
Purification of the crude product obtained by chromatography on silica gel with petroleum ether (volume ratio 3:97) gave 4-chlorodifluoromethoxybenzoic acid trans-.
4- (trans-4-propylcyclohexyl) cyclohexyl ester was obtained. Melting point (C-S): 65 ° C,
(S-N): 103 ° C, clearing point (N-I): 150.5
° C.

The following compounds could be prepared in an analogous manner:

4-chlorodifluoromethoxybenzoic acid trans-4- (trans-4-pentylcyclohexyl) cyclohexyl ester, 3-fluoro-4-chlorodifluoromethoxybenzoic acid trans-4- (trans-4-propylcyclohexyl) cyclohexyl ester , 4-chlorodifluoromethoxybenzoic acid trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexyl ester, 3-fluoro-
4-chlorodifluoromethoxybenzoic acid trans-4-
[2- (trans-4-propylcyclohexyl) ethyl] cyclohexyl ester, 4-chlorodifluoromethoxybenzoic acid 4- (trans-4-propylcyclohexyl) phenyl ester, 4-chlorodifluoromethoxybenzoic acid 4- (trans-4- Pentylcyclohexyl) phenyl ester, 3-fluoro-4-chlorodifluoromethoxybenzoic acid 4- (trans-4-propylcyclohexyl) phenyl ester.

Example 9 A solution of 3 g of 4- (trans-4-pentylcyclohexyl) benzoyl chloride in 5 ml of pyridine was treated with 1.9 g of 4-chlorodifluoromethoxyphenol and the mixture was stirred at room temperature for 12 hours. Then, the reaction mixture was poured into ice cold water and extracted with diethyl ether. The organic phase was extracted successively with 10% hydrochloric acid, saturated sodium bicarbonate solution and water, then dried over magnesium sulphate, filtered and concentrated. Ethyl acetate / petroleum ether (volume ratio 3:
The crude product obtained by chromatography on silica gel with 97) was purified to give 4- (trans-4-pentylcyclohexyl) benzoic acid 4-chlorodifluoromethoxyphenyl ester. Melting point (C-N): 11
3.4 ° C, clearing point (N-I): 143.3 ° C.

The following compounds could be prepared in an analogous manner:

4- (trans-4-propylcyclohexyl) benzoic acid 4-chlorodifluoromethoxyphenyl ester, 4- (trans-4-propylcyclohexyl) benzoic acid 3-fluoro-4-chlorodifluoromethoxyphenyl ester, 4- ( Trans-4-pentylcyclohexyl) benzoic acid 3-fluoro-4-chlorodifluoromethoxyphenyl ester, 4- [2- (trans-4-propylcyclohexyl) ethyl] benzoic acid 4-chlorodifluoromethoxyphenyl ester, 4-
[2- (trans-4-propylcyclohexyl) ethyl] benzoic acid 3-fluoro-4-chlorodifluoromethoxyphenyl ester.

Example 10 Several binary mixtures (BM) were prepared from 4- (trans-4-pentylcyclohexyl) benzonitrile and in each case the compound of formula (I), the clearing point, V ₁₀ , t
_The effects on _off and Δ _n were investigated. V ₁₀ and t _off
Is 22 ° C in a TN cell with a plate spacing of 8 μm.
The response time was measured at a value 2.5 times V ₁₀ .
Pure 4- (trans-4-pentylcyclohexyl)
The corresponding values for benzonitrile are: Clearing point (N-I): 54.6 ° C., V ₁₀ = 1.62 V
, T _0ff = 42 ms, Δ _n = 0.120.

BM-1 10% by weight of 4-chlorodifluoromethoxy-4'-
(4-trans-propylcyclohexyl) biphenyl, 90% by weight of 4- (trans-4-pentylcyclohexyl) benzonitrile; clearing point (NI): 55.
7 ° C., V ₁₀ = 1.58 V, t _off = 47 ms, Δ _n =
0.123.

BM-2 20% by weight of 4-chlorodifluoromethoxy-4'-
(4-trans-propylcyclohexyl) biphenyl, 80% by weight of 4- (trans-4-pentylcyclohexyl) benzonitrile; clearing point (N-I): 57.
9 ° C., V ₁₀ = 1.56 V, t _off = 52 ms, Δ _n =
0.125.

BM-3 10% by weight of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 90% by weight of 4- (trans-4-pentylcyclohexyl) benzo Nitrile;
Clearing point (N-I): 57.7 ° C., V ₁₀ = 1.61 V, t
_off = 44 ms, Δ _n = 0.120.

BM-4 20% by weight of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -4-chlorodifluoromethoxybenzene, 80% by weight of 4- (trans-4-pentylcyclohexyl) benzo Nitrile;
Clearing point (N-I): 60.5 ° C., V ₁₀ = 1.62 V, t
_off = 48 ms, Δ _n = 0.116.

BM-5 10% by weight of 1-{[trans-4- (trans-4-
Pentylcyclohexyl) cyclohexyl] methoxy}
-4-chlorodifluoromethoxybenzene, 90% by weight
4- (trans-4-pentylcyclohexyl) benzonitrile; clearing point (N-I): 58.9 ° C., V ₁₀ =
1.63 V, t _0ff = 50 ms, Δ _n = 0.120.

BM-6 20% by weight of 1-{[trans-4- (trans-4-
Pentylcyclohexyl) cyclohexyl] methoxy}
-4-chlorodifluoromethoxybenzene, 80% by weight
4- (trans-4-pentylcyclohexyl) benzonitrile; clearing point (N-I): 63.6 ° C., V ₁₀ =
1.67 V, t _0ff = 63 ms, Δ _n = 0.116.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C07C 69/773 C07C 69/773 69/82 69/82 A 69/86 69/86 69/92 69/92 255/54 255/54 C07D 213 / 30 C07D 213/30 213/46 213/46 239/26 239/26 239/34 239/34 239/52 239/52 319/06 319/06 C09K 19/30 C09K 19/30 19/34 19/34 G02F 1/13 500 G02F 1/13 500 (72) Inventor Richard Beheckel Zeher 8008, Switzerland, Zurich, Felsenstraße 10 (72) Inventor Martin Schatt Zeher 4411 Zeltisberg, Riesterrel Strasse 77 (72) Inventor Yury A. Fiarkov Ukraine, 252021 Kyiv, Frat 3, Oktober Revolution Street 13/4 (72) Inventor Svetlana Buj Shelyatenko Ukraine, 252035 Kyiv, Furat 7. Kudry Shova Street 2 (72) Inventor Ascha I. Paburchenko Russia, 123448 Moskow, Frat 38, M. Zhukov Prospect 62 Em (72) Inventor Natalia I. Smirnova Russia, 141700 Dolgopurdny Moskov Region , Fred 89, Likhacheskoskoye Schoshe 13-1 (72) Inventor Vladimir Ef Petrov Russia, 123007 Moskow, Fred 87, Koloshevskoye Schosse 66 (56) References JP-A-55- 111480 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, A ¹ and A ² are each independently a trans-
1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or unsubstituted or with fluorine, cyano and / or methyl Represents mono- or di-substituted 1,4-phenylene; Z ¹ and Z ² are
Each independently represent a single _{bond, -CH 2 CH 2 -, -} CH 2
_{O -, - OCH 2 -,} - C≡C -, - COO -, - OO
_{C -, - (CH 2)} 4 -, - O (CH 2) 3 -, - (C
H _{2) 3} O-, or trans, -CH = CH -, -
_{CH = CH (CH 2) 2} -, - (CH 2) 2 CH = CH
-, - CH = CHCH ₂ O- or -OCH ₂ CH =
Represents CH-; R is alkyl or alkenyl having 1 to 12 carbon atoms or 2 to 12 carbon atoms, respectively (optionally 1 to 3 hydrogen atoms may be substituted with fluorine; and / or 1 to Two non-adjacent CH ₂ groups may be replaced by O); and X ¹ , X ² and X
³ each independently represents hydrogen or fluorine; provided that (a) ring A ¹ is not saturated when ring A ² is a (hetero) aromatic ring, and / or (b) 2 Z ¹ and Z ² between the (hetero) aromatic rings of represent a covalent single bond, —COO— or —OOC—, and / or (c) substituent X ¹ .
2 or less of X ² and X ³ represent fluorine). 2. General formulas (Ia) to (Ik): (Wherein X ¹ , X ² , X ³ , Z ¹ , Z ² and R have the same meanings as in claim 1). 3. One of the groups Z ¹ and Z ² is a single bond or --C.
≡C-, and the other of the groups Z ¹ and Z ² is a single bond,
_{-CH 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - C
3. A compound according to claim 1 or 2, which also represents .tbd.C-, -COO-, OOC- or trans -CH = CH- between two non-aromatic rings. 4. A compound according to claim 1, 2 or 3 in which the residues R each have a chain length of 1 to 7 or 2 to 7 carbon atoms. 5. The compound according to claim 1, wherein the residue R has a chain length of 2 to 5 carbon atoms. 6. The compound according to claim ¹ , wherein X ¹ , X ² and X ³ represent hydrogen. 7. X ¹ and X ³ represent hydrogen and X ²
The compound according to any one of claims 1 to 5, wherein is fluorine. 8. A liquid crystal mixture wherein at least one component is a compound of general formula (I) as defined in claim 1. 9. Use of a compound as defined in claim 1 for optical or electro-optical purposes. 10. A method of using the liquid crystal mixture according to claim 8 for optical or electro-optical purposes.