JPH0640968A - Butene derivative - Google Patents

Abstract

PURPOSE:To provide a new compound exhibiting a low viscosity and a high elastic constant ratio, excellent in compatibility and heat resistance and useful for a liquid crystal display device, etc. CONSTITUTION:A compound of formula I (R is a 1 to 10C alkyl; X, Y and Z are each H, a halogen, cyano, a halogen-substituted methyl or a halogen- substituted methoxy; A is 1-butene-1,4-diyl or 3-butene-1,4-diyl), e.g. 1-[4'-(4''- cyanophenyl)cyclohexyl]-4-(4'-ethylcyclohexyl)-E-butene. In addition, the compound of formula I can be obtained, e.g. by reacting an aldehyde derivative of formula II with a phosphorous ylide of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a butene derivative, and more particularly to a novel compound having a butenediyl group sandwiched between cyclohexane rings in the molecule and useful as a liquid crystal material, and a liquid crystal composition containing the compound.

[0002]

2. Description of the Related Art Display elements using liquid crystals are widely used in watches, calculators and the like. These liquid crystal display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystal substances. The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase, of which the one using the nematic liquid crystal is most widely put into practical use. Further, as the display method applied to the liquid crystal display, TN (twisted nematic) type, DS (dynamic scattering) type, and guest are used for the electro-optical effect. There are host type and DAP type. Although many liquid crystalline compounds including those in the research stage are known to date, no substance is currently used as a single liquid crystalline substance enclosed in a display element. The reason for this is that the liquid crystal substance expected as a display element material is preferably one that exhibits a liquid crystal phase in a wide range of temperature in nature, especially at room temperature, which is most frequently used as a display element. This is because it must be sufficiently stable against factors and have sufficient physical characteristics to drive a display element, whereas no single substance satisfying these conditions has been found. . Therefore, at present, a composition having such characteristics is prepared by mixing several kinds of liquid crystal substances or further non-liquid crystal substances and put into practical use as a material.

These liquid crystal compositions are required to be stable against moisture, light, heat, air and the like which are usually present in the environment of use. It also requires stability to electric fields and electromagnetic radiation, and also that the liquid crystal compounds to be mixed are chemically stable in the environment of use. Further, the liquid crystal composition needs to have appropriate values of various physical properties such as optical anisotropy value, dielectric anisotropy value and electric conductivity depending on the display system and the shape of the device. In particular, recently, the importance of a substance having low optical anisotropy as a material for a thin film transistor (TFT) type liquid crystal display device has been increasing.

In order to meet such demands, simple liquid crystal compounds having various properties have been developed, and in particular, as a physical property for improving the viscosity and the optical anisotropy value, the molecular cross-linking portion has flexibility. Compounds bearing the are found. For example, a compound having a two-carbon chain in the central part of the molecule is disclosed in JP-A-61-215336, and a compound having the same four-carbon chain as an intermediate group is described in West German Laid-Open Patent Publication (DE) 40278.
40 and JP-A-3-66632. There are almost no examples of a liquid crystal compound having a 4-carbon chain containing an unsaturated bond as an intermediate group, which has been known so far.
6632 only describes one substance as a synthetic intermediate. However, the substituted styrene derivative as described in JP-A-3-66632 is thermally unstable and cannot be used in a normal environment. The present inventors have also conducted research aiming at the development of such a new material, and have found a new material (Japanese Patent Application No. 4-11035).
1). The above compounds are collectively shown below.

[0005]

However, none of the above-mentioned compounds provide all the physical properties required by a single compound, and the development of compounds exhibiting even more excellent properties is required. Was there.

[0006]

[Chemical 2]

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors to solve the above-mentioned problems, as a result of comparison with a generally known liquid crystal compound having a novel structure represented by the following general formula (I), To find a compound having improved properties, and completed the present invention.

[0008]

[Chemical 3]

(In the formula, R represents an alkyl group having 1 to 10 carbon atoms, X, Y and Z are each independently a hydrogen atom,
Represents a halogen atom, a cyano group, a methyl group substituted with 1 to 3 halogens or a methoxy group substituted with 1 to 3 halogens, and A represents 1-butene-1,4-diyl or 3-butene- The compound of the present invention, which represents a 1,4-diyl group, eliminates the problem of thermal stability by setting the unsaturated portion at a position adjacent to the non-aromatic ring, and has a characteristic of a 4-carbon chain having an unsaturated bond. It is a new liquid crystal material with a structure that makes the most of Due to this peculiar structure, the compound of the present invention has appropriate rigidity and degree of freedom as compared with the conventional compounds, facilitates alignment in the liquid crystal phase, and has a relatively high elastic constant ratio. Further, the compound of the present invention, even though having a highly flexible butenediyl group in the molecule, forms a liquid crystal phase in a wide temperature range, has an appropriate optical anisotropy value, and has a viscosity of Characterized by a very low point. Further, the compound of the present invention is chemically and thermally stable, and does not deteriorate even under the conditions of electromagnetic radiation, voltage application and the like. The butenediyl group, which is an intermediate group of the compound of the present invention, has two isomers, E and Z. Of these, the E form generally shows more preferable physical properties than the Z form. When the compound of the present invention is used as a component of a liquid crystal composition, the compound of the present invention has excellent compatibility with other liquid crystal materials and enables the construction of a new liquid crystal display device having significant characteristics. The compound of the present invention makes the liquid crystal characteristics variable by converting a ring structure and a cyclic substituent. Among the compounds of the present invention, the following compounds can be mentioned as preferred compounds.

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

Of these preferred compounds, Ib, Ih, In, Ibb, Ih having a cyano group
And compounds of I-nn obtain a large dipole moment, and I-c having a trifluoromethyl group,
I-i, I-o, I-cc, I-ii and I-oo
Is suitable as a compound having a reduced viscosity and a large polarizability. Further, among the compounds of the present invention, those having a halogen atom as a substituent on the phenyl ring are preferable from the viewpoint of increasing the dielectric constant. Among the compounds of the present invention, the alkyl group represented by R in the general formula (I) has 2 to 5 carbon atoms.
The thing of the thing is preferable from the point of expanding a liquid crystal range.

The liquid crystal composition provided by the present invention is
In addition to the component (A) containing at least one compound represented by formula (I), a component (B) containing one or more compounds having high dielectric constant anisotropy, preferably Δε> 5, | Δε | < 5
The component (C) containing at least one compound having a low dielectric anisotropy, or the component (D) containing at least one compound having a clearing point above 80 ° C., and optionally other components (E). ) Is contained in the dielectric liquid crystal composition.

Particularly preferred compounds as the component (B) are shown below.

[0017]

[Chemical 8]

[0018]

[Chemical 9]

Here, R represents an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two nonadjacent carbon atoms of the group may be replaced by an oxygen atom. The compounds particularly preferable as the component (C) are shown below.

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

Here, R and R'represent an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two nonadjacent carbon atoms of the group may be replaced by an oxygen atom. The compounds particularly preferable as the component (D) are shown below.

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

[0031]

[Chemical 20]

[0032]

[Chemical 21]

[0033]

[Chemical formula 22]

Here, R and R'represent an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two nonadjacent carbon atoms of the group may be replaced by an oxygen atom. Particularly preferred compounds as the component (E) are shown below.

[0035]

[Chemical formula 23]

[0036]

[Chemical formula 24]

Here, R represents an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two nonadjacent carbon atoms of the group may be replaced by an oxygen atom. The composition according to the present invention preferably contains one or more compounds of the formula (I) in a proportion of 0.1 to 40% by weight in terms of excellent liquid crystal properties.

(Production Method) The compound of the present invention can be synthesized, for example, by the reaction formula shown below.

[0039]

[Chemical 25]

That is, in the compound of the present invention, A is -CH = CH-CH ₂ CH.
_{When 2-} is represented, the general formula (IV)

[0041]

[Chemical formula 26]

An aldehyde derivative represented by the formula (wherein X, Y and Z have the same meanings as described above), and a general formula (V)

[0043]

[Chemical 27]

The compound can be synthesized by reacting a phosphorus ylide compound represented by the formula (wherein R represents the same meaning as described above). In the compounds of the present invention, A is -CH
_{When 2} CH ₂ -CH = CH- is represented, the general formula (II)

[0045]

[Chemical 28]

An aldehyde derivative represented by the formula (wherein X, Y and Z have the same meanings as described above) and a compound represented by the general formula (I
II)

[0047]

[Chemical 29]

It can be synthesized by reacting with a phosphorus ylide compound represented by the formula (wherein R represents the same meaning as described above). The reaction of the general formulas (II) and (III) or the reaction of the general formulas (IV) and (V) is
The reaction proceeds easily by using the specific method described in c Reaction Vol 14,270 (1965). That is, it is a precursor of the phosphorus ylide compound represented by the general formula (III) or (V) in a suitable solvent, the general formula (VI) or (VII)

[0049]

[Chemical 30]

(In the formula, R has the same meaning as described above, and Ha
l represents a halogen atom) is converted into a phosphorus ylide compound in the system by using an appropriate base and is treated with an aldehyde derivative represented by the general formula (II) or (IV). . The phosphonium salts of (VI) and (VII) are easily obtained from the corresponding halogen compounds and triphenylphosphine, and the phosphonium salts can be used after isolation or as they are. The base used in this case is potassium t
-Butoxide, sodium methoxide, sodium hydride, sodium dimcyl, n-butyllithium, lithium diisopropylamide, pyridine, triethylamine and the like can be used, but the generated phosphorus ylide compound (III) or (V) is at room temperature. Since it is stable and has a good yield, potassium t-butoxide, sodium methoxide, sodium hydride, sodium dimcyl,
N-butyllithium is preferable, and potassium t-butoxide is preferable because it is easy to prepare and easy to handle. Preparation of phosphorus ylide compound (III) or (V),
The subsequent reaction with the aldehyde derivative (II) or (IV) is preferably carried out in a solvent because it is easy to handle and the temperature can be easily adjusted. Usually phosphorus ylide compound (II
The preparation of I) or (V) and the reaction of the generated ylide with the aldehyde derivative (II) or (IV) are continuously carried out in the same solvent. As the solvent that can be used in this case, any solvent that does not inhibit the reaction may be used, and for example, diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, hexane, heptane, dimethylsulfoxide, dimethylformamide, and the like are preferable. It can be used as a single solvent or a mixed solvent. The reaction temperature in this reaction is -50 ° C.
Is selected from the range of the boiling point of the solvent, but the reaction proceeds rapidly, and side reactions are difficult to proceed, so 0 ° C to 5 ° C.
More preferably between 0 ° C.

The compound of the present invention produced by the reaction of the general formulas (II) and (III) or the general formulas (IV) and (V) is generally obtained as a mixture of its stereoisomers, which mixture is subjected to silica gel column chromatography, The compound of the present invention having a more preferable stereochemistry can be obtained by a separation operation such as high performance liquid chromatography, but if necessary, the stereoisomer of the compound of the present invention is more preferable, for example, by the method described in Tetrahedron Vol 36, pp 577. It can be converted into a compound of the present invention. The following method will be given as a specific example of this three-dimensional inversion.

[0052]

[Chemical 31]

A mixture of stereoisomers of the compound of the present invention or only a stereoisomer of the compound of the present invention is converted to an oxirane derivative using a peracid, and then converted to a 1,2-dihalide by using a brominating agent. Erythro halide is obtained more selectively and in high yield. By reducing the obtained dihalide with a suitable reducing agent such as iron or zinc, it is possible to convert it into a mixture containing a more preferable stereoisomer of the compound of the present invention in a predominant ratio. Further, this mixture can be recrystallized from a suitable solvent to obtain the compound of the present invention composed of only a single isomer. As the peracid used when a mixture of stereoisomers of the compound of the present invention or only the stereoisomer of the compound of the present invention is converted to an oxirane derivative using peracid, mCPBA (metachloroperbenzoic acid), peracetic acid, and formic acid, Although perbenzoic acid and the like can be mentioned, mCPBA which is easy to handle and stable is most preferable. The amount of peracid used is 1-1.1 with respect to the olefin substrate.
Five times equivalents are preferred. This oxirane formation reaction is desirably carried out in a solvent, and any solvent that can be used may be used as long as it does not inhibit the reaction, and methylene chloride, chloroform, xylene, toluene, ethyl acetate, ether,
Tetrahydrofuran etc. are mentioned. Of these, methylene chloride and chloroform are more preferable because of the good solubility of the substrate and the reagent. The present oxidation reaction is generally carried out from 0 ° C to the boiling point range of the solvent, but it is preferable to operate from 0 ° C to around room temperature, which does not require a device such as heating and special cooling, from the viewpoint of easy operation. Further, this reaction is remarkably promoted by adding a suitable base. As the base used, potassium carbonate, sodium hydrogen carbonate, sodium acetate, sodium hydroxide,
Potassium hydroxide, pyridine, triethylamine and the like can be mentioned, but alkali metal carbonates are particularly preferable from the viewpoint that side reactions are difficult to proceed. The base is used in an excess amount of 2 to 3 times equivalent except when the substrate is weak to the base.
When the oxirane derivative is converted into erythrodibromide using a brominating agent, the brominating agent used is triphenylphosphine dibromide, hydrogen bromide, phosphorus bromide, thionyl bromide, N-bromosuccinimide, carbon tetrabromide- Examples thereof include triphenylphosphine. Of these, triphenylphosphine dibromide, phosphorus bromide and the like are preferable because of rapid reaction and good selectivity. These brominating agents are usually used in 1 to 1.5 times equivalent amount.

This bromination reaction is preferably carried out in an inert solvent, and the solvent selected is toluene, benzene, dioxane, tetrahydrofuran or the like. Of these, toluene, dioxane and the like are preferable because they have proper boiling points. Further, this reaction is preferably carried out at a temperature between −50 ° C. and the boiling point of the solvent, more preferably from room temperature to the boiling point range of the solvent in that the reaction proceeds rapidly. The crude dibromide product thus produced can be isolated in only the required steric form by recrystallization from an appropriate solvent. The recrystallization operation follows a usual method. The isolated erythro-form dibromide can be converted to the compound of the present invention having a preferred configuration by reduction treatment. This conversion reaction is a reaction with a reducing agent such as zinc or reduced iron in a polar or non-polar solvent. Examples of the solvent used in this reaction include acetic acid, hydrochloric acid, and a mixed solvent system with a commonly used organic solvent that can be mixed with these. Examples of the reducing agent used in this reaction include zinc dust and reduced iron. The thus-produced composition organism of the compound of the present invention having the preferred configuration can be made pure by carrying out purification procedures generally used if necessary. Typical purification operations include liquid chromatography, recrystallization, distillation and the like.

The general formula (VIII) used as a starting material for the synthesis of the compound of the present invention

[0056]

[Chemical 32]

(In the formulae, X, Y and Z have the same meanings as described above, and n is the general formula (I) in which A is -CH = CH.
CH ₂ CH ₂ — represents 2 and A is —CH ₂ C.
A compound represented by H ₂ CH = CH- represents 0) is generally synthesized by the following method.

[0058]

[Chemical 33]

Among the compounds represented by the general formula (VIII), the compound in which n is 0 follows the following method. That is, the general formula (IX)

[0060]

[Chemical 34]

(Wherein X, Y and Z have the same meanings as described above, and Hal 'represents a chlorine, bromine or iodine atom), a so-called Grignard produced by treating a halobenzene derivative with metallic magnesium. By reacting a reagent with 1,4-cyclohexanedione monoethylene ketal, the compound of the general formula (X)

[0062]

[Chemical 35]

(In the formula, X, Y and Z have the same meanings as described above) and converted to the alcohol form. This reaction can be carried out by using a generally well-known method described in Organic Reactions 8, 28 (1954) and the like. Alcohol obtained by this reaction
(X) is a compound represented by the general formula (XI) by dehydration using a suitable acid and a solvent.

[0064]

[Chemical 36]

(Wherein X, Y and Z have the same meanings as described above) and can be efficiently converted into a cyclohexene derivative. Examples of the solvent used for this conversion include toluene, xylene, benzene, ethyl acetate, heptane, hexane, chloroform and methylene chloride. The acid catalyst used in this reaction includes paratoluenesulfonic acid, benzenesulfonic acid, phosphoric acid, hydrochloric acid,
Sulfuric acid or ion exchange resin can be used.
The amount of acid used at this time can be selected from the range of 1 to 2% to the same amount. Further, this reaction is significantly accelerated by using a dehydration apparatus represented by Dean Stark's apparatus. The compound (XI) thus obtained is hydrogenated using a conventional catalytic reduction method to give the compound of the general formula (XII)

[0066]

[Chemical 37]

(In the formula, X, Y and Z have the same meanings as described above) and converted to a phenylcyclohexane derivative. This hydrogenation reaction is carried out in a hydrogen atmosphere using a heterogeneous catalyst such as platinum oxide, platinum-carbon, palladium-carbon, palladium-black or a homogeneous catalyst represented by Wilkinson's catalyst in a solvent which is stable against hydrogenation. To be done. In this case, the hydrogen supply is from normal pressure to 20 Katm.
However, since it does not require a device such as an autoclave, it is preferably performed at normal pressure. The compound (XII) thus obtained was Green; Protective
Groups in Organic Synthesis 116,1980 (JOHN WILEY
& SONS) using the general method described in
III)

[0068]

[Chemical 38]

(Wherein X, Y and Z have the same meanings as described above), and converted to a phenylcyclohexanone derivative. Further, by reacting this with methoxymethyltriphenylphosphine ylide, the compound of the general formula (XIV)

[0070]

[Chemical Formula 39]

(Wherein X, Y and Z have the same meanings as described above) and can be converted to methyl vinyl ether. This conversion method is described in Chem. Ber., 95, 2514 (1962).
Follow normal conditions described in. The compound (XIV) thus obtained can be converted to the desired compound (VIII) by treating with an acid in a water-containing solvent. This conversion method uses a substrate and hydrochloric acid, sulfuric acid, solid acid, etc. in a mixed solvent of aprotic polar solvent such as ethanol or methanol or an aprotic polar solvent such as acetone, dioxane, tetrahydrofuran or dimethylformamide and an amount of water that does not cause phase separation. Can be carried out in a system in which The reaction proceeds rapidly and gives the target compound (VIII) immediately in the range of 0 ° C to room temperature.

The compound represented by the general formula (VIII) in which n is 2 can be obtained by the following method. That is, the compound represented by the above general formula (XIII) is 1,
An intermediate of the general formula (XV) by treatment with 3-dioxan-2-ylethyltriphenylphosphine ylide.

[0073]

[Chemical 40]

A compound represented by the formula (wherein X, Y and Z have the same meanings as described above) is obtained. This reaction is Synthe
sis, 132 (1979). In addition, the compound (XV) thus obtained is hydrogenated using a conventional catalytic reduction method to give a compound of the general formula (XVI)

[0075]

[Chemical 41]

(In the formula, X, Y and Z have the same meanings as described above) and converted to a phenylcyclohexane derivative. This hydrogenation reaction is carried out in a hydrogen atmosphere using a heterogeneous catalyst such as platinum oxide, platinum-carbon, palladium-carbon, palladium-black or a homogeneous catalyst represented by Wilkinson's catalyst in a solvent that is stable against hydrogenation. To do. In this case, hydrogen is supplied in the range of atmospheric pressure to 20 Katm, but it is desirable to supply it under atmospheric pressure because no device such as an autoclave is required. Hydrogenated product (XVI)
Green; Protective Groups in Organic Synthesis 11
6,1980 (JOHN WILEY & SONS) can be converted into the general formula (VIII), which is a raw material of the compound of the present invention where n is 2, by using the general method described in JOHN WILEY & SONS.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0078]

【Example】

Example 1 Synthesis of 1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl) -E-butene 3- (4'-ethylcyclohexyl) propyl iodide (5.6g , 20 mmol) and triphenylphosphine (5.2 g, 20 mmol) in xylene (20 m
It was dissolved in 1) and stirred with heating under reflux for 12 hours. After cooling the reaction solution to room temperature, potassium-t-butoxide (2.0
g, 18 mmol) was added and the mixture was further stirred for 1 hour. 4- (4'-cyanophenyl) cyclohexanecarbaldehyde (2.66 g, 12.5 m)
A solution of (mol) in tetrahydrofuran (5 ml) was added dropwise. This was further stirred at room temperature for 3 hours, and then ether (1
0 ml) was added and left to stand. The precipitated crystals were removed by filtration and the resulting solution was concentrated under reduced pressure. The obtained light brown oily matter was isolated and purified by silica gel column chromatography to give a mixture of isomers of the title compound (4.0
5 g) was obtained.

The obtained isomer mixture of the title compound was dissolved in methylene chloride (200 ml) and potassium carbonate (6 g,
43 mmol) and metachloroperbenzoic acid (3.0
g, 17 mmol) was added and the mixture was stirred at room temperature for 2 hours. After completion of stirring, the reaction solution was poured into a sodium thiosulfate solution and extracted with methylene chloride (100 ml). The organic layer was washed with water and then dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure to give 1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl) -1,
A crude product of 2-butene oxide (4.4 g) was obtained. This product was used in the next reaction without purification.

1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl)
Crude product of -1,2-butene oxide (4.4 g) and triphenylphosphine dibromide (10 g, 24 m)
(mol) was dissolved in toluene (500 ml), and the mixture was stirred with heating under reflux for 2 hours. After completion of stirring, the reaction solution was treated with a silica gel short column and then concentrated under reduced pressure to obtain a yellow oily substance. The resulting oily substance was recrystallized from a mixed solvent system of ethanol / methanol to give erythro-1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl) -1,2-dibromo. Butane (3.1g)
Got

Dibromobutane body and zinc dust (3.0
g, 46 mmol) in acetic acid (50 ml) was stirred at room temperature for 3 hours. Insoluble matter was removed from the reaction solution by filtration, water was added to the resulting solution, and this was added with ether (50 m
Extracted in l). The obtained organic layer was washed with water and then concentrated under reduced pressure to obtain a colorless oily substance. This product was purified by silica gel column chromatography and then recrystallized from a heptane-ethanol mixed solvent system to give white crystals (1.3 g).
Got

Melting point 90.9-91.7 ° C., clearing point 15
6.0 to 156.8 ° C. Similarly, the following compounds are synthesized. 1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(4" -cyanophenyl) cyclohexyl) -4- (4 ' -Prolcyclohexyl) -E-butene 1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene 1- (4'-(4" -cyanophenyl) ) Cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene Example 2 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-fluorophenyl) cyclohexanecarbaldehyde From 1-
(4 '-(4 "-fluorophenyl) cyclohexyl)
-4- (4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-fluorophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(4" -fluorophenyl) cyclohexyl) -4- (4 ' -Ethylcyclohexyl) -E-butene 1- (4 '-(4 "-fluorophenyl) cyclohexyl) -4- (4'-propylcyclohexyl) -E-butene 1- (4'-(4" -fluorophenyl) Cyclohexyl) -4- (4′-butylcyclohexyl) -E-butene Example 3 According to the method of Example 1, 1 from 3- (4′-pentylcyclohexyl) propyl bromide and 4- (4′-chlorophenyl) cyclohexanecarbaldehyde -(4 '
-(4 "-chlorophenyl) cyclohexyl) -4-
(4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-chlorophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(4" -chlorophenyl) cyclohexyl) -4- (4'-ethyl Cyclohexyl) -E-butene 1- (4 '-(4 "-chlorophenyl) cyclohexyl) -4- (4'-propylcyclohexyl) -E-butene 1- (4'-(4" -chlorophenyl) cyclohexyl) -4 -(4'-Butylcyclohexyl) -E-butene Example 4 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-trifluoromethylphenyl) cyclohexanecarbaldehyde to 1- (4- (4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl)- E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-methylcyclohexyl)
-E-butene 1- (4 '-(4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-ethylcyclohexyl)
-E-butene 1- (4 '-(4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-propylcyclohexyl) -E-butene 1- (4'-(4" -trifluoromethylphenyl) Cyclohexyl) -4- (4'-butylcyclohexyl)
-E-Butene Example 5 According to the method of Example 1, from 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-trifluoromethoxyphenyl) cyclohexanecarbaldehyde to 1- (4 '-(4 "- Trifluoromethoxyphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4'-propylcyclohexyl) -E-butene 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene Example 6 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-difluoromethoxyphenyl) cyclohexanecarbaldehyde according to the method of Example 1. This gives 1- (4- (4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-methylcyclohexyl)
-E-butene 1- (4 '-(4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-ethylcyclohexyl)
-E-butene 1- (4 '-(4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-propylcyclohexyl) -E-butene 1- (4'-(4" -difluoromethoxyphenyl) cyclohexyl) -4- (4'-butylcyclohexyl)
-E-butene Example 7 1- (4 '-(3 ") from 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3', 4'-difluorophenyl) cyclohexanecarbaldehyde according to the method of Example 1. , 4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 ", 4" -difluorophenyl) cyclohexyl) -4- (4'-methylcyclohexyl)-
E-butene 1- (4 '-(3 ", 4" -difluorophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl)-
E-butene 1- (4 '-(3 ", 4" -difluorophenyl) cyclohexyl) -4- (4'-propylcyclohexyl)
-E-butene 1- (4 '-(3 ", 4" -difluorophenyl) cyclohexyl) -4- (4'-butylcyclohexyl)-
E-Butene Example 8 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3'-fluoro-
1- (4 '-(3 "-fluoro-4" -cyanophenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained from 4'-cyanophenyl) cyclohexanecarbaldehyde.

Similarly, the following compounds are synthesized. 1- (4 '-(3 "-fluoro-4" -cyanophenyl) cyclohexyl) -4- (4-methylcyclohexyl) -E-butene 1- (4'-(3 "-fluoro-4" -cyanophenyl ) Cyclohexyl) -4- (4-ethylcyclohexyl) -E-butene 1- (4 ′-(3 ″ -fluoro-4 ″ -cyanophenyl) cyclohexyl) -4- (4-propylcyclohexyl) -E-butene 1 -(4 '-(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -4- (4-butylcyclohexyl) -E-butene Example 9 According to the method of Example 1, 3- (4'-pentylcyclohexyl) Propyl bromide and 4- (3'-fluoro-
1- (4 '-(3 "-fluoro-4" -chlorophenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained from 4'-chlorophenyl) cyclohexanecarbaldehyde.

Similarly, the following compounds are synthesized. 1- (4 ′-(3 ″ -fluoro-4 ″ -chlorophenyl) cyclohexyl) -4- (4-methylcyclohexyl) -E-butene 1- (4 ′-(3 ″ -fluoro-4 ″ -chlorophenyl) cyclohexyl ) -4- (4-Ethylcyclohexyl) -E-butene 1- (4 '-(3 "-fluoro-4" -chlorophenyl) cyclohexyl) -4- (4-propylcyclohexyl) -E-butene 1- (4 '-(3 "-Fluoro-4" -chlorophenyl) cyclohexyl) -4- (4-butylcyclohexyl) -E-butene Example 10 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4 -(3'-fluoro-
From 4'-trifluoromethylphenyl) cyclohexanecarbaldehyde to 1- (4 '-(3 "-fluoro-
4 "-trifluoromethylphenyl) cyclohexyl)
-4- (4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 "-fluoro-4" -trifluoromethylphenyl) cyclohexyl-4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3 "-fluoro-4"- Trifluoromethylphenyl) cyclohexyl-4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(3 "-fluoro-4" -trifluoromethylphenyl) cyclohexyl-4- (4'-propylcyclohexyl) ) -E-Butene 1- (4 ′-(3 ″ -fluoro-4 ″ -trifluoromethylphenyl) cyclohexyl-4- (4′-butylcyclohexyl) -E-butene Example 11 According to the method of Example 1 3 -(4'-pentylcyclohexyl) propyl bromide and 4- (3'-fluoro-
From 4'-trifluoromethoxyphenyl) cyclohexanecarbaldehyde to 1- (4 '-(3 "-fluoro-
4 ″ -trifluoromethoxyphenyl) cyclohexyl) -4- (4′-pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 "-fluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3 "-fluoro-4" -Trifluoromethoxyphenyl) cyclohexyl) -4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(3 "-fluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -4- (4' -Propylcyclohexyl) -E-butene 1- (4 '-(3 "-fluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene Example 12 Example 1 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3'-fluoro-
From 4'-difluoromethoxyphenyl) cyclohexanecarbaldehyde to 1- (4 '-(3 "-fluoro-
4 ″ -difluoromethoxyphenyl) cyclohexyl)
-4- (4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 "-fluoro-4" -difluoromethoxyphenyl) cyclohexyl-4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3 "-fluoro-4" -difluoro Methoxyphenyl) cyclohexyl-4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(3 "-fluoro-4" -difluoromethoxyphenyl) cyclohexyl-4- (4'-propylcyclohexyl) -E -Butene 1- (4 '-(3 "-fluoro-4" -difluoromethoxyphenyl) cyclohexyl-4- (4'-butylcyclohexyl) -E-butene Example 13 3- (4' according to the method of Example 1 -Pentylcyclohexyl) propyl bromide and 4- (3 ', 4', 5 '
-Trifluorophenyl) cyclohexanecarbaldehyde to 1- (4 '-(3 ", 4", 5 "-trifluoromethoxyphenyl) cyclohexyl) -4- (4'-
Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3", 4 ", 5 "-Trifluorophenyl) cyclohexyl) -4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(3", 4 ", 5" -trifluorophenyl) cyclohexyl) -4- (4' -Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene Example 14 Example 1 From 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-cyanophenyl) cyclohexanecarbaldehyde according to the method of 1- (4'- 3 ", 5" - difluoro-4 "- cyanophenyl) cyclohexyl) -4-
(4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 ", 5" -difluoro-4 "-cyanophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3", 5 "- Difluoro-4 ″ -cyanophenyl) cyclohexyl) -4- (4′-ethylcyclohexyl) -E-butene 1- (4 ′-(3 ″, 5 ″ -difluoro-4 ″ -cyanophenyl) cyclohexyl) -4- (4'-Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-cyanophenyl) cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene Example 15 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-chlorophenyl) cyclohexanecarboalde 1- (4 '-(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -4- from hydr
(4'-Pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -4- (4'-methylcyclohexyl) -E-butene 1- (4'-(3", 5 "-difluoro -4 ″ -chlorophenyl) cyclohexyl) -4- (4′-ethylcyclohexyl) -E-butene 1- (4 ′-(3 ″, 5 ″ -difluoro-4 ″ -chlorophenyl) cyclohexyl) -4- (4 ′ -Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -4- (4'-butylcyclohexyl) -E-butene Example 16 Example 1 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexane according to the method of 1- (4 '-(3 ", 5" from carboxaldehyde
-Difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained. Similarly, the compounds shown below are synthesized.

1- (4 '-(3 ", 5" -difluoro-
4 "-trifluoromethylphenyl) cyclohexyl)
-4- (4'-methylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'
-Ethylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'
-Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'
-Butylcyclohexyl) -E-butene Example 17 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-trifluoromethoxyphenyl) cyclohexanecarbo according to the method of Example 1. From aldehyde, 1- (4 '-(3 ",
5 ″ -difluoro-4 ″ -trifluoromethoxyphenyl) cyclohexyl) -4- (4′-pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4-
(4'-Methylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4-
(4'-Ethylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4-
(4'-Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4-
(4'-Butylcyclohexyl) -E-butene Example 18 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-difluoromethoxyphenyl) 1- (4 '-(3 ", 5" from cyclohexanecarbaldehyde
-Difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene is obtained Similarly, the compounds shown below are synthesized.

1- (4 '-(3 ", 5" -difluoro-
4 ″ -difluoromethoxyphenyl) cyclohexyl)
-4- (4'-methylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'
-Ethylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'
-Propylcyclohexyl) -E-butene 1- (4 '-(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -4- (4'
-Butylcyclohexyl) -E-butene Example 19 Synthesis of 4- (4 '-(4 "-cyanophenyl) cyclohexyl) -1- (4'-pentylcyclohexyl) -E-butene 4-pentylcyclohexylmethyl bromide (12 .4
g, 50 mmol) and triphenylphosphine (1
3.1 g, 50 mmol) was dissolved in xylene (100 ml), and the mixture was stirred with heating under reflux for 12 hours. The reaction solution was cooled to room temperature and the precipitated crystals (22.4 g) were isolated by filtration. Tetrahydrofuran (200 m
l) and the mixture was stirred at room temperature, potassium t-butoxide (5.0 g, 44 mmol) was added, and the mixture was further stirred for 1 hr. 3- (4 '-(4 "-
(Cyanophenyl) cyclohexyl) propanal (9.
A solution of 6 g, 43 mmol) in tetrahydrofuran (50 ml) was added dropwise. This was further stirred at room temperature for 3 hours, then ether (50 ml) was added and the mixture was allowed to stand. The precipitated crystals were removed by filtration, and the resulting solution was concentrated under reduced pressure.
The obtained light brown oily matter was isolated and purified using silica gel column chromatography to obtain an isomer mixture (10.0 g) of the title compound.

The resulting isomer mixture of the title compounds (6.
6 g) was dissolved in methylene chloride (300 ml), potassium carbonate (8 g, 58 mmol) and metachloroperbenzoic acid (4.3 g, 25 mmol) were added, and the mixture was stirred at room temperature for 2 hours. After completion of stirring, the reaction solution was poured into a sodium thiosulfate solution and extracted with methylene chloride (200 ml). The organic layer was washed with water and then dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure to give 4- (4 '-(4 "-cyanophenyl) cyclohexyl) -1- (4'-pentylcyclohexyl).
A crude product of -1,2-butene oxide (7.0 g) was obtained. This product was used in the next reaction without purification.

Crude product of 1- (4 '-(4 "-cyanophenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -1,2-butene oxide (7.0 g)
And triphenylphosphine dibromide (10.0
g, 24 mmol) was dissolved in toluene (500 ml), and the mixture was stirred with heating under reflux for 2 hours. After completion of stirring, the reaction solution was treated with a silica gel short column and then concentrated under reduced pressure to obtain a yellow oily substance. The obtained oily substance was recrystallized from an ethanol / methanol mixed solvent system to give erythro-4- (4 '-(4 "
-Cyanophenyl) cyclohexyl) -1- (4'-pentylcyclohexyl) -1,2-dibromobutane (6.68 g, 12 mmol) was obtained.

A suspension of dibromobutane derivative (6.5 g) and zinc dust (5.0 g, 76 mmol) in acetic acid (200 ml) was stirred at room temperature for 3 hours. Insoluble matters were removed from the reaction solution by filtration, water was added to the obtained solution, and this was extracted with ether (200 ml). The obtained organic layer was washed with water and then concentrated under reduced pressure to obtain a colorless oily substance. This was purified by silica gel column chromatography and then recrystallized from a heptane-ethanol mixed solvent system to obtain white crystals (2.5 g).

Melting point 82.9-84.0 ° C., clearing point
163.8 to 164.5 ° C. Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(4 "-Cyanophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(4 ″ -Cyanophenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(4 "-Cyanophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(4 ″ -Cyanophenyl) cyclohexyl) -E-butene Example 20 4-pentylcyclohexylmethyl bromide and 3- (4 ′-(4 ″ -fluorophenyl) cyclohexyl) propanal according to the method of Example 19 to 1- ( 4'-Pentylcyclohexyl) -4- (4 '-(4 "-fluorophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(4 "-Fluorophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(4 ″ -Fluorophenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(4 ″ -fluorophenyl) cyclohexyl) -E-butene 1- (4′-butylcyclohexyl) -4- (4′-
(4 ″ -Fluorophenyl) cyclohexyl) -E-butene Example 21 From 4-pentylcyclohexylmethyl bromide and 3- (4 ′-(4 ″ -chlorophenyl) cyclohexyl) propanal according to the method of Example 19 to 1- (4 ′ -Pentylcyclohexyl) -4- (4 ′-(4 ″ -chlorophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(4 ″ -chlorophenyl) cyclohexyl) -E-butene Example 22 From 4-pentylcyclohexylmethyl bromide and 3- (4 ′-(4 ″ -trifluoromethylphenyl) cyclohexyl) propanal according to the method of Example 19 to 1-
(4'-Pentylcyclohexyl) -4- (4'-
(4 ″ -trifluoromethylphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(4 ″ -Trifluoromethylphenyl) cyclohexyl) -E-butene Example 23 1- (4 from 4-pentylcyclohexylmethyl bromide and 4- (4′-trifluoromethoxyphenyl) cyclohexylpropanal according to the method of Example 19. ´－
(4 ″ -trifluoromethoxyphenyl) cyclohexyl) -4- (4′-pentylcyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4′-methylcyclohexyl) -E-butene 1- (4 ′-(4 ″ -trifluoromethoxyphenyl)
Cyclohexyl) -4- (4'-ethylcyclohexyl) -E-butene 1- (4 '-(4 "-trifluoromethoxyphenyl)
Cyclohexyl) -4- (4′-propylcyclohexyl) -E-butene 1- (4 ′-(4 ″ -trifluoromethoxyphenyl)
Cyclohexyl) -4- (4′-butylcyclohexyl) -E-butene Example 24 4-Pentylcyclohexylmethyl bromide and 3- (4 ′-(4 ″ -difluoromethoxyphenyl) cyclohexyl) propanal according to the method of Example 19. From 1-
(4'-Pentylcyclohexyl) -4- (4'-
(4 ″ -difluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(4 "-Difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(4 "-Difluoromethoxyphenyl) cyclohexyl) -E-butene Example 25 4-Pentylcyclohexylmethyl bromide and 3- (4 '-(3", 4 "-difluorophenyl) cyclohexyl) propanal according to the method of Example 19. From 1-
(4'-Pentylcyclohexyl) -4- (4'-
(3 ", 4" -difluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 4" -difluorophenyl) cyclohexyl)
-E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 4" -difluorophenyl) cyclohexyl)
-E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 4" -difluorophenyl) cyclohexyl)
-E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 4" -difluorophenyl) cyclohexyl)
-E-Butene Example 26 From 4-pentylcyclohexylmethyl bromide and 4-3- (3 "-fluoro-4" -cyanophenyl) cyclohexyl) propanal according to the method of Example 19 to 1-
(4'-Pentylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -cyanophenyl) cyclohexyl) -E-butene Example 27 4-Pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4" according to the method of Example 19).
-Chlorophenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl) -4- (4'-
(3 ″ -Fluoro-4 ″ -chlorophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -chlorophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ″ -Fluoro-4 ″ -chlorophenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(3 "-fluoro-4" -chlorophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 "-Fluoro-4" -chlorophenyl) cyclohexyl) -E-butene Example 28 4-Pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4" according to the method of Example 19).
-Trifluoromethylphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl)-
4- (4 '-(3 "-fluoro-4" -trifluoromethylphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ″ -fluoro-4 ″ -trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4′-ethylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4′-butylcyclohexyl) -4- (4′-
(3 ″ -Fluoro-4 ″ -trifluoromethylphenyl) cyclohexyl) -E-butene Example 29 4-Pentylcyclohexylmethyl bromide and 3- (4 ′-(3 ″ -fluoro-4 ″) according to the method of Example 19
-Trifluoromethoxyphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl)
-4- (4 '-(3 "-fluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ″ -fluoro-4 ″ -trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-ethylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-butylcyclohexyl) -4- (4′-
(3 "-Fluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -E-butene Example 30 4-Pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4" according to the method of Example 19
-Difluoromethoxyphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl)-
4- (4 '-(3 "-fluoro-4" -difluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ″ -fluoro-4 ″ -difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-ethylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-propylcyclohexyl) -4- (4′-
(3 ″ -fluoro-4 ″ -difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4′-butylcyclohexyl) -4- (4′-
(3 "-Fluoro-4" -difluoromethoxyphenyl) cyclohexyl) -E-butene Example 31 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 ", 4", 5 "according to the method of Example 19). -Trifluorophenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl) -4- (4 '
-(3 ", 4", 5 "-trifluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -E-butene Example 32 4-Pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "-difluoro according to the method of Example 19). -4 ″ -cyanophenyl) cyclohexyl) propanal to 1- (4′-pentylcyclohexyl) -4-
(4 ′-(3 ″, 5 ″ -difluoro-4 ″ -cyanophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-cyanophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-cyanophenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-cyanophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 5" -Difluoro-4 "-cyanophenyl) cyclohexyl) -E-butene Example 33 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "-according to the method of Example 19). Difluoro-4 ″ -chlorophenyl) cyclohexyl) propanal to 1- (4′-pentylcyclohexyl) -4-
(4 ′-(3 ″, 5 ″ -difluoro-4 ″ -chlorophenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 5" -Difluoro-4 "-chlorophenyl) cyclohexyl) -E-butene Example 34 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "-difluoro according to the method of Example 19 -4 ″ -trifluoromethylphenyl) cyclohexyl) propanal to 1- (4′-pentylcyclohexyl) -4- (4 ′-(3 ″, 5 ″ -difluoro-4 ″)
-Trifluoromethylphenyl) cyclohexyl) -E
-Obtain butene.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 5" -Difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -E-butene Example 35 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 according to the method of Example 19). "-Difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl) -4- (4 '-(3 ", 5" -difluoro-
4 ″ -trifluoromethoxyphenyl) cyclohexyl) -E-butene is obtained.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 5" -Difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -E-butene Example 36 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 according to the method of Example 19 ″ -Difluoro-4 ″ -difluoromethoxyphenyl) cyclohexyl) propanal to 1- (4′-pentylcyclohexyl) -4- (4 ′-(3 ″, 5 ″ -difluoro-4 ″)
-Difluoromethoxyphenyl) cyclohexyl) -E
-Obtain butene.

Similarly, the following compounds are synthesized. 1- (4'-methylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-ethylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-propylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene 1- (4'-butylcyclohexyl) -4- (4'-
(3 ", 5" -difluoro-4 "-difluoromethoxyphenyl) cyclohexyl) -E-butene Example 37 (Application Example 1) Liquid crystal composition 1083 manufactured by Merck & Co.
-(4-Pentylcyclohexyl) -4- (4'-
15% of (4 ″ -cyanophenyl) cyclohexyl) -E-butene was dissolved and its physical properties were measured.
= 69.4 ° C., Δε = 10.4, Δn = 0.125, η
₂₀ = 24.9, Vth = 1.71, K ₃₃ / K ₁₁ = 2.1
9, K ₃₃ / K ₂₂ = 2.71. Further, this composition was left in a freezer at -20 ° C for 20 days, but no precipitation of crystals was observed. Example 38 (Use Example 2) One of the compounds of the present invention was used in the liquid crystal composition 1083 manufactured by Merck & Co., Inc.
-(4 '-(4 "-cyanophenyl) cyclohexyl)
Add 4- (4-ethylcyclohexyl) -E-butene to 1
It was dissolved by 5% and the physical properties were measured. As a result Cp = 6
6.5 ° C., Δε = 10.5, Δn = 0.125, η ₂₀ =
25.1, Vth = 1.66, K ₃₃ / K ₁₁ = 2.05, K
It was ₃₃ / K ₂₂ = 2.83. Also, this composition is -20
It was left in a freezer at 0 ° C for 20 days, but no precipitation of crystals was observed. Example 39 (Use Example 3) One of the compounds of the present invention was used in the liquid crystal composition 1083 manufactured by Merck & Co., Inc.
-(4 '-(3 "fluoro-4-cyanophenyl) cyclohexyl) -4- (4-ethylcyclohexyl) -E
-Butene was dissolved by 15% and the physical properties were measured. As a result, Cp = 64.4 ° C., Δε = 11.2, Δn = 0.12
1, η ₂₀ = 26.7, Vth = 1.53, K ₃₃ / K ₁₁ =
2.11, was K ₃₃ / K ₂₂ = 2.53. Further, this composition was left in a freezer at -20 ° C for 20 days, but no precipitation of crystals was observed.

[0121]

INDUSTRIAL APPLICABILITY The compound of the present invention eliminates the problem of thermal stability by setting the unsaturated portion at the adjacent position of the non-aromatic ring, and has a unique structure of a 4-carbon chain having an unsaturated bond. , A moderate rigidity and degree of freedom are obtained compared to the conventional ones, alignment in the liquid crystal phase is facilitated, a relatively high elastic constant ratio is provided, and a highly flexible butenediyl group is incorporated into the molecule. Despite having it, it forms a liquid crystal phase in a wide temperature range, has a suitable optical anisotropy value, has a very low viscosity, and is chemically and thermally stable. No deterioration occurs under the conditions of electromagnetic radiation, voltage application, etc. Further, when the compound of the present invention is used as a component of a liquid crystal composition, it has excellent compatibility with other liquid crystal materials and can be used in a wide temperature range without increasing the viscosity. It enables the construction of a new liquid crystal display device having various characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location G02F 1/13 500 9225-2K (72) Inventor Tomoyuki Kondo 2-17 Tatsumidai Higashi, Ichihara, Chiba C- 104 (72) Inventor Yasuyuki Goto 462-2 Nishihiro, Ichihara-shi, Chiba

Claims (2)

[Claims] 1. A general formula: (In the formula, R represents an alkyl group having 1 to 10 carbon atoms,
X, Y and Z each independently represent a hydrogen atom, a halogen atom, a cyano group, a methyl group substituted with 1 to 3 halogens or a methoxy group substituted with 1 to 3 halogens, and A is 1 -Butene-1,4-diyl or 3-butene-1,4-diyl group). 2. At least one compound according to claim 1.
A liquid crystal composition containing at least one kind.