JP3183361B2 - Butene derivative - Google Patents

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 useful as a liquid crystal material having a butenediyl group sandwiched between cyclohexane rings in the molecule, and a liquid crystal composition containing the compound.

[0002]

2. Description of the Related Art Display devices using liquid crystals are widely used in watches, calculators and the like. These liquid crystal display elements utilize optical anisotropy and dielectric anisotropy of a liquid crystal material. The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase. Among them, a liquid crystal phase using a nematic liquid crystal is most widely used. In addition, display methods applied to liquid crystal displays include TN (twisted nematic) type, DS (dynamic scattering) type, and guest for electro-optic effect. There are host type, DAP type, etc. Many liquid crystal compounds, including those at the research stage, have been known to date, but at present, there is no substance that is used as a single liquid crystal substance encapsulated in a display element. This is because a liquid crystal substance expected as a display element material is preferably a substance which exhibits a liquid crystal phase in a wide temperature range as possible, especially at room temperature, which is most frequently used as a display element, in the natural world. This is because it must be sufficiently stable against factors and have physical properties sufficient to drive the display element, but no single substance satisfying these conditions has been found. . Therefore, at present, a composition having such characteristics by mixing several kinds of liquid crystal substances or further non-liquid crystal substances is prepared and put to practical use as a material.

[0003] These liquid crystal compositions are required to be stable to moisture, light, heat, air and the like which are usually present in a use environment. It also requires stability to electric fields and electromagnetic radiation, and that the liquid crystal compounds to be mixed are chemically stable in the environment of use. Further, in the liquid crystal composition, various physical property values such as an optical anisotropy value, a dielectric anisotropy value, and an electric conductivity need to take appropriate values depending on a display method and an element shape. 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 viscosity and optical anisotropy, flexibility in a molecular crosslinked portion has been developed. Was found. For example, a compound having a two-carbon chain in the center of the molecule is disclosed in JP-A-61-215336, and a compound having the four-carbon chain as an intermediate group is disclosed in West German Published Patent Application (DE) 40278.
40 and JP-A-3-66632. There has been almost no example of a liquid crystal compound having a 4-carbon chain containing an unsaturated bond as an intermediate group, and there is almost no example in JP-A-3-6.
6632 describes only 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 for the purpose of developing such a new material, and have found a new material (Japanese Patent Application No. 4-11035).
1). The above compounds are summarized below.

[0005]

However, none of the above-mentioned compounds still provides all the physical properties required by a single compound alone, and there is a need for the development of a compound exhibiting more excellent properties. I was

[0006]

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[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have compared with a generally known liquid crystal compound having a novel structure represented by the following general formula (I). Thus, the present invention has been completed by finding a compound having improved properties.

[0008]

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Wherein R represents an alkyl group having 1 to 10 carbon atoms, X, Y and Z each independently represent a hydrogen atom,
A 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 to the position adjacent to the non-aromatic ring, and has the characteristic of a 4-carbon chain having an unsaturated bond. It is a new liquid crystal material having a structure that makes use of Due to this unique structure, the compound of the present invention has an appropriate rigidity and degree of freedom as compared with those of the prior art, facilitates orientation in a liquid crystal phase, and has a relatively high elastic constant ratio. In addition, the compound of the present invention forms a liquid crystal phase in a wide temperature range despite having a butenediyl group having high flexibility in the molecule, has an appropriate optical anisotropy value, and has a viscosity. It is characterized by a very low point. The compound of the present invention is chemically and thermally stable, and does not deteriorate at all under conditions such as electromagnetic radiation and voltage application. The butenediyl group, which is the intermediate group of the compound of the present invention, has two isomers, E and Z, of which the E-form generally exhibits more preferable physical properties than the Z-isomer. 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 changing the ring structure and the cyclic substituent. Preferred compounds among the compounds of the present invention include the following.

[0010]

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[0011]

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[0012]

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[0013]

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Among these preferred compounds, Ib, Ih, In, Ibb, and Ihh having a cyano group are preferred.
And I-nn compounds obtain a large dipole moment, and Ic having a trifluoromethyl group,
Ii, Io, 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.
Are preferred in that the liquid crystal range is expanded.

The liquid crystal composition provided by the present invention comprises:
In addition to the component (A) containing at least one compound represented by the formula (I), a component (B) containing one or more compounds having high dielectric anisotropy, preferably ΔΔ> 5, | Δε | < 5
Component (C) containing one or more compounds having low dielectric anisotropy, component (D) containing one or more compounds having a clearing point exceeding 80 ° C., and other components (E) if necessary. ).

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

[0017]

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[0018]

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

[0020]

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[0021]

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[0022]

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

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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

[0035]

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[0036]

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

(Production method) The compound of the present invention can be synthesized, for example, by the following reaction formula.

[0039]

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

[0041]

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Wherein X, Y and Z have the same meanings as described above, and a compound represented by the general formula (V)

[0043]

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(Wherein, R represents the same meaning as described above). In the compound of the present invention, A is -CH
_{When 2} CH ₂ -CH = CH- is represented by the general formula (II)

[0045]

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

[0047]

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(Wherein R has the same meaning as described above), and can be synthesized by reacting with a phosphorus ylide compound represented by the formula: The reaction of general formulas (II) and (III) or the general formulas (IV) and (V)
c Easily proceeds by using the specific method described in Reaction Vol 14, 270 (1965). That is, the compound represented by the general formula (VI) or (VII) which is a precursor of the phosphorus ylide compound represented by the general formula (III) or (V) in an appropriate solvent

[0049]

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(Wherein R has the same meaning as described above;
wherein l represents a halogen atom), a phosphorus ylide compound is derived in a system using an appropriate base, and treated with an aldehyde derivative represented by the general formulas (II) and (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, dimsyl sodium, n-butyllithium, lithium diisopropylamide, pyridine, triethylamine and the like can be used, but the generated phosphorus ylide compound (III) or (V) can be used at room temperature. Potassium t-butoxide, sodium methoxide, sodium hydride, dimsyl sodium,
N-butyllithium is preferred, and potassium t-butoxide is preferred because it is easy to adjust and easy to handle. Adjusting phosphorus ylide compound (III) or (V),
The subsequent reaction with the aldehyde derivative (II) or (IV) is preferably carried out in a solvent because the handling is easy and the temperature can be easily adjusted. Usually, phosphorus ylide compounds (II
The adjustment of I) or (V) and the reaction between the generated ylide and the aldehyde derivative (II) or (IV) are carried out continuously in the same solvent. The solvent that can be used in this case may be any solvent that does not hinder the reaction, and examples thereof include diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, hexane, heptane, dimethyl sulfoxide, and dimethylformamide. 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 quickly and the side reaction hardly progresses.
More preferably between 0 ° C.

The compounds of the invention formed by the reaction of the general formulas (II) and (III) or of the general formulas (IV) and (V) are generally obtained as a mixture of their stereoisomers, which mixture can be obtained by 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 by the method described in Tetrahedron Vol36, pp577, for example. It can be converted to the compound of the present invention. As a specific example of the three-dimensional inversion, the following method is given.

[0052]

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By converting a mixture of the stereoisomers of the compound of the present invention or only the stereoisomer of the compound of the present invention into an oxirane derivative using a peracid, and then converting it into a 1,2-dihalide using a brominating agent, An erythrodi halide is obtained more selectively and in high yield. By reducing the obtained dihalide with an appropriate reducing agent such as iron or zinc, it is possible to convert the dihalide into a mixture containing more preferable stereoisomers of the compound of the present invention in a superior ratio. The mixture can be recrystallized from an appropriate solvent to obtain the compound of the present invention composed of only a single isomer. The peracid used when a mixture of the 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 a peracid is mCPBA (metachloroperbenzoic acid), peracetic acid, formic acid, Although perbenzoic acid and the like can be mentioned, mCPBA which is easy to handle and is stable is most preferable. The amount of peracid used is 1 to 1.
Five equivalents are preferred. The present oxiranation reaction is desirably performed in a solvent, and any solvent that can be used is not limited as long as it does not inhibit the reaction. Methylene chloride, chloroform, xylene, toluene, ethyl acetate, ether,
Tetrahydrofuran and the like. Of these, methylene chloride and chloroform are more preferred because of good solubility of the substrate and the reagent. The present oxidation reaction is generally carried out in the range from 0 ° C. to the boiling point of the solvent. However, the temperature is preferably from 0 ° C. to around room temperature, which does not require a device such as heating or special cooling, because the operation is simple. This reaction is remarkably promoted by adding an appropriate 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 because side reactions hardly proceed. The amount of the base used is an excess of 2 to 3 equivalents, unless the substrate is particularly weak to the base.
When the oxirane derivative is converted into erythrobromide using a brominating agent, the brominating agent used may be triphenylphosphine dibromide, hydrogen bromide, phosphorus bromide, thionyl bromide, N-bromosuccinimide, carbon tetrabromide- Triphenylphosphine and the like. Of these, triphenylphosphine dibromide, phosphorus bromide, and the like are preferable because of quick reaction and good selectivity. These brominating agents are usually used in an equivalent amount of 1 to 1.5 times.

This bromination reaction is preferably carried out in an inert solvent, and toluene, benzene, dioxane, tetrahydrofuran and the like are used as the selected solvent. Of these, toluene, dioxane, and the like are preferable because the boiling point region is appropriate. This reaction is preferably carried out at a temperature between −50 ° C. and the boiling point of the solvent, but more preferably at room temperature to the boiling point of the solvent in that the reaction proceeds promptly. The crude dibromide thus produced can be isolated only in the required three-dimensional 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 preferable configuration by reduction treatment. This conversion reaction is to react 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-formed composition of the compound of the present invention having a preferred configuration can be purified, if necessary, by commonly used purification procedures. Typical purification operations include liquid chromatography, recrystallization, distillation and the like.

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

[0056]

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(Wherein, X, Y and Z have the same meanings as described above, and n is the general formula (I) wherein A is -CH = CH
When CH ₂ CH ₂ — represents 2, A represents —CH ₂ C
Compounds represented by represents 0 when representing the H ₂ CH = CH-) is synthesized generally by the following method.

[0058]

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Among the compounds represented by the general formula (VIII), the compound wherein n is 0 is according to the following method. That is, the general formula (IX)

[0060]

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

[0062]

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

[0064]

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(Wherein, X, Y and Z have the same meanings as described above). Solvents used in this conversion include toluene, xylene, benzene, ethyl acetate, heptane, hexane, chloroform, methylene chloride and the like. The acid catalyst used in this reaction includes paratoluenesulfonic acid, benzenesulfonic acid, phosphoric acid, hydrochloric acid,
Sulfuric acid or an ion exchange resin can be used.
The amount of the acid used at this time can be selected from a range of 1 to 2% to an equivalent amount. This reaction is remarkably accelerated by using a dehydration apparatus such as the Dean-Stark apparatus. The compound (XI) thus obtained is hydrogenated by a commonly used catalytic reduction method to give a compound of the formula (XII)

[0066]

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(Wherein X, Y and Z have the same meanings as described above). This hydrogenation reaction is carried out under 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 stable to hydrogenation. It is performed. In this case, the supply of hydrogen is from normal pressure to 20 Katm.
However, since it does not require an apparatus such as an autoclave, it is desirable to carry out the reaction at normal pressure. Compound (XII) thus obtained was obtained from Green; Protective
Groups in Organic Synthesis 116,1980 (JOHN WILEY
& SONS) using the general method described in (X)
III)

[0068]

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(Wherein, X, Y and Z have the same meanings as described above). This is further reacted with methoxymethyltriphenylphosphine ylide to give a compound of the general formula (XIV)

[0070]

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

The compound represented by the general formula (VIII) wherein n is 2 is obtained according to the following method. That is, the compound represented by the above general formula (XIII) is
By treating with 3-dioxan-2-ylethyltriphenylphosphine ylide, an intermediate represented by the general formula (XV)

[0073]

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(Wherein X, Y and Z have the same meanings as described above). This reaction is Synthe
sis, 132 (1979). The compound (XV) thus obtained is hydrogenated by a commonly used catalytic reduction method to give a compound of the formula (XVI)

[0075]

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(Wherein X, Y and Z have the same meanings as described above). This hydrogenation reaction is carried out under a hydrogen atmosphere using a heterogeneous catalyst such as platinum oxide, platinum-carbon, palladium-carbon, palladium-black or a homogeneous catalyst typified by Wilkinson catalyst in a solvent stable to hydrogenation. Do. In this case, the supply of hydrogen is carried out in the range from normal pressure to 20 Katm, but it is preferable to supply hydrogen at normal pressure because an apparatus such as an autoclave is not required. The hydride (XVI)
Green; Protective Groups in Organic Synthesis 11
6,1980 (JOHN WILEY & SONS) can be converted to the general formula (VIII) which is a raw material of the compound of the present invention wherein n is 2.

Hereinafter, the present invention will be described more specifically 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 (5.6 g) , 20 mmol) and triphenylphosphine (5.2 g, 20 mmol) in xylene (20 m
1) and stirred under reflux for 12 hours. After the reaction solution was cooled to room temperature, potassium-t-butoxide (2.0
g, 18 mmol) and further stirred for 1 hour. The reaction solution having a red color was added to 4- (4'-cyanophenyl) cyclohexanecarbaldehyde (2.66 g, 12.5 m
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. After removing the precipitated crystals by filtration, the resulting solution was concentrated under reduced pressure. The obtained light brown oil was isolated and purified using silica gel column chromatography, and an isomer mixture of the title compound (4.0) was obtained.
5 g) were 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) and stirred at room temperature for 2 hours. After completion of the 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 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 was used for the next reaction without performing purification operation.

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

The dibromobutane compound and zinc powder (3.0
g, 46 mmol) in acetic acid (50 ml) was stirred at room temperature for 3 hours. The insoluble matter was removed from the reaction solution by filtration, water was added to the obtained 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 oil. This was purified using silica gel column chromatography and then recrystallized from a heptane-ethanol mixed solvent system to give white crystals (1.3 g).
I got

Melting point 90.9 to 91.7 ° C., clearing point 15
6.0 to 156.8 ° C. The following compounds are synthesized in the same manner. 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 procedure 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 was obtained 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, 1- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-trifluoromethylphenyl) cyclohexanecarbaldehyde (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, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-trifluoromethoxyphenyl) cyclohexanecarbaldehyde are used to give 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 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (4'-difluoromethoxyphenyl) cyclohexanecarbaldehyde To give 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 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 4'-difluorophenyl) cyclohexanecarbaldehyde are converted to 1- (4'-(3 " , 4 "-Difluoromethoxyphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene.

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, 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, 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, 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 According to the method of Example 1, 3- (4' -Pentylcyclohexyl) propyl bromide and 4- (3 ', 4', 5 '
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 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 15 According to the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-chlorophenyl) cyclohexanecarbaldehyde From the hide, 1- (4 '-(3 ", 5" -difluoro-4 "-chlorophenyl) cyclohexyl) -4-
(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 1- (4 '-(3 ", 5")
-Difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4- (4'-pentylcyclohexyl) -E-butene The following compounds are synthesized in the same manner.

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 Following the method of Example 1, 3- (4'-pentylcyclohexyl) propyl bromide and 4- (3 ', 5'-difluoro-4'-trifluoromethoxyphenyl) cyclohexanecarbo. 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 The following compounds are synthesized in the same manner.

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. After cooling the reaction solution to room temperature, the precipitated crystals (22.4 g) were isolated by filtration. The obtained white crystals were washed with tetrahydrofuran (200 m
l), 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 hour. 3- (4 '-(4 "-) was added to the red reaction solution.
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, and ether (50 ml) was added, and the mixture was allowed to stand. After the precipitated crystals were removed by filtration, the resulting solution was concentrated under reduced pressure.
The obtained light brown oil was isolated and purified using silica gel column chromatography to obtain an isomer mixture (10.0 g) of the title compound.

An isomer mixture of the obtained title compound (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 the 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 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 was used for the next reaction without performing purification operation.

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 under heating and reflux for 2 hours. After completion of the stirring, the reaction solution was treated with a silica gel short column, and then concentrated under reduced pressure to obtain a yellow oil. The obtained oil 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 the 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 the solution was extracted with ether (200 ml). The obtained organic layer was washed with water and then concentrated under reduced pressure to obtain a colorless oil. This was purified using 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., clear 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 1- (4-pentylcyclohexylmethyl bromide and 3- (4 '-(4" -fluorophenyl) cyclohexyl) propanal according to the method of Example 19. 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 1- (4) from 4-pentylcyclohexylmethyl bromide and 3- (4 '-(4" -chlorophenyl) cyclohexyl) propanal according to the method of Example 19. '-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 1-From 4-pentylcyclohexylmethyl bromide and 3- (4 '-(4" -trifluoromethylphenyl) cyclohexyl) propanal according to the method of Example 19.
(4′-pentylcyclohexyl) -4- (4′-
(4 "-trifluoromethylphenyl) cyclohexyl) -E-butene is obtained.

The following compounds are synthesized in the same manner. 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.

The following compounds are synthesized in the same manner. 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.

In the same manner, 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.

In the same manner, 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 1-from 4-pentylcyclohexylmethyl bromide and 4-3- (3 "-fluoro-4" -cyanophenyl) cyclohexyl) propanal according to the method of Example 19.
(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 Following the procedure of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4").
-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 Following the procedure of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4").
-From 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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4").
From -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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 "-fluoro-4").
-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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3 ", 4", 5 "). -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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "-difluoro -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 Following the procedure of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "- 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 Following the procedure of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 "-difluoro -4 "-trifluoromethylphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl) -4- (4 '-(3", 5 "-difluoro-4"
-Trifluoromethylphenyl) cyclohexyl) -E
Obtaining 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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 From "-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 Following the method of Example 19, 4-pentylcyclohexylmethyl bromide and 3- (4 '-(3", 5 From "-difluoro-4" -difluoromethoxyphenyl) cyclohexyl) propanal to 1- (4'-pentylcyclohexyl) -4- (4 '-(3 ", 5" -difluoro-4 "
-Difluoromethoxyphenyl) cyclohexyl) -E
Obtaining 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
-(4-pentylcyclohexyl) -4- (4'-
15% of (4 "-cyanophenyl) cyclohexyl) -E-butene was dissolved and the physical properties thereof 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. The 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 added to a liquid crystal composition 1083 manufactured by Merck.
-(4 '-(4 "-cyanophenyl) cyclohexyl)
4- (4-ethylcyclohexyl) -E-butene is
After 5% dissolution, 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. Further, the composition was changed to -20.
After standing in a freezer at 20 ° C. for 20 days, no precipitation of crystals was observed. Example 39 (Use Example 3) One of the compounds of the present invention was added to a liquid crystal composition 1083 manufactured by Merck.
-(4 '-(3 "fluoro-4-cyanophenyl) cyclohexyl) -4- (4-ethylcyclohexyl) -E
-Butene was dissolved at 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. The composition was left in a freezer at -20 ° C for 20 days, but no precipitation of crystals was observed.

[0121]

The compound of the present invention eliminates the problem of thermal stability by setting the unsaturated portion at the position adjacent to the non-aromatic ring, and has a unique structure of a 4-carbon chain having an unsaturated bond. But, it has a moderate rigidity and flexibility compared to the conventional ones, facilitates alignment in the liquid crystal phase, has a relatively high elastic constant ratio, and has a highly flexible butenediyl group in the molecule. Despite having, it forms a liquid crystal phase in a wide temperature range, has an appropriate optical anisotropy value, has a very low viscosity, and is chemically and thermally stable. No deterioration occurs even under conditions such as electromagnetic radiation and voltage application. 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 range of temperature without increasing the viscosity. It enables the construction of a new liquid crystal display device having various characteristics.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomoyuki Kondo 2-17-17 Tatsumidaihigashi, Ichihara-shi, Chiba Prefecture (72) Inventor Yasuyuki Goto 462-2 Nishihiro, Ichihara-shi, Chiba Prefecture (56) References JP Hei 5-310605 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) CA (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (Wherein, 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; -Butene-1,4-diyl or 3-butene-1,4-diyl group). 2. The method according to claim 1, wherein at least one
Liquid crystal compositions containing more than one type.