JPH08245441A - Liquid crystal compound containing fluoro-substituted alkyl group and liquid crystal composition - Google Patents

Abstract

PURPOSE: To obtain an electrochemically stable liquid crystal compound large in Δε value, and highly compatible with existing liquid crystal compounds, to obtain a liquid crystal composition containing this compound, and to obtain a liquid crystal display element using this composition. CONSTITUTION: This liquid crystal compound is expressed by general formula F-(CH)n -E-(CH2 CH2 )k -G-(CH2 CH2 )l -L-(CH2 CH2 )m (n is an integer of 1 10; k, l and m are each an integer of 0-2; ring E is 1,4-cyclohexylene group or 1,4- phenylene group where at least one hydrogen atom on the six-membered ring may be substituted with fluorine atom; G and L are each a covalent bond, or 1,4-cyclohexylene group or 1,4-phenylene group where at least one hydrogen atom on the six-membered ring may be substituted with fluorine atom; ring Z is (F-substituted) 1,4-phenylene group; Q is a covalent bond or O; Y is a 1-3C fluoroalkyl group or F; when ring E is 1,4-cyclohexylene group and G and/or L is covalent bond(s), (k+l+m)≠0 and when Q is O, Y is not F).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal compound effective as a component of a liquid crystal composition, particularly a liquid crystal compound suitable for use in a liquid crystal composition for TFT, a liquid crystal composition containing the same and a liquid crystal composition thereof. The present invention relates to a liquid crystal composition constituted by using.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal material. Depending on its display mode, TN type (twisted nematic type), DS type (dynamic scattering type) are used. ), Guest-host type, DAP type (alignment phase change type), STN type, etc., and the properties of the liquid crystal substance suitable for each use are different. Recently, a liquid crystal display element having a higher display quality has been particularly demanded, and in order to meet the demand, a thin film transistor (TF) is used.
There is an increasing demand for active matrix type display devices represented by T). The liquid crystal substance used in any of the display elements needs to be stable to moisture, air, heat, light, etc., and exhibits a liquid crystal phase in a temperature range as wide as possible around room temperature, has a low viscosity, and It must have good solubility, a large dielectric anisotropy value (Δε), and an optimum refractive index anisotropy value (Δn). However, at present, there is no substance that satisfies all such conditions with a single compound, and at present the liquid crystal composition obtained by mixing several kinds of liquid crystal compounds and non-liquid crystal compounds is used.

A characteristic particularly required for the TFT type liquid crystal display device is to maintain a high contrast during the frame time. Therefore, the liquid crystal material used for this purpose has a specific resistance value in addition to the above conditions. Is required to be large. Recently, a TFT type liquid crystal display element is required to be driven at a low voltage.
A liquid crystal compound or a liquid crystal composition having a larger Δε than the liquid crystal material used for the FT type liquid crystal display element has been required.

Many of the general liquid crystalline compounds have a cyano group, but when used in a TFT type liquid crystal display element, the cyano group decomposes when a high voltage is applied, so that a high specific resistance value is exerted during the display operation. I can't keep up. Therefore, a liquid crystal compound containing a cyano group cannot be used for a TFT type liquid crystal display device, despite having a high Δε. In order to improve this, a liquid crystal material having a high specific resistance value and a high Δε has been actively developed. A fluorine-based compound is suitable as the liquid crystal compound having a high specific resistance value. These compounds, generally liquid crystal compounds having a fluorine atom as a substituent, are known as follows. For example, Japanese Patent Publication No. 02-40048 discloses a compound represented by the following formula (1).

[0005]

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The compound (1) is industrially used because it has a higher specific resistance than a compound having a cyano group, but it has a small Δε of about 4 and cannot be driven at a sufficiently low voltage. Absent. Greater Δε than the above compound (1)
JP-A-02-233626 discloses a trifluorophenyl compound represented by the following formula (2) as a compound having

[0007]

[Chemical 9]

However, this compound only shows an insufficient Δε of about 8 and the fluorine atom is added to the above (1).
Since it has a structure in which a larger amount than that of the compound of the formula is introduced, the temperature range of the liquid crystal phase is extremely narrow and it is unsuitable as one component constituting the liquid crystal composition. Further regarding the NI point, 1- (4-propylcyclohexyl) -4- (3,4,5-trifluorophenyl) cyclohexane of the formula example (2) is 1- (4) which is a monofluoro compound example. −
Propylcyclohexyl) -4- (4-fluorophenyl) cyclohexane is about 60 ° C., which is a difluoro compound example, 1- (4-propylcyclohexyl) -4-
It has been confirmed that the temperature is lower by about 25 ° C. than that of (3,4-difluorophenyl) cyclohexane.

Further, in Japanese Patent Laid-Open No. 04-506361,
The compounds represented by the following formulas (3) and (4) are disclosed.

[0010]

[Chemical 10]

These compounds have relatively large Δε (for example, Δε of compounds (4) and (5) is about 7).
However, the compatibility with existing liquid crystalline compounds at low temperatures was extremely poor, and it was unsuitable as a constituent component of a liquid crystal composition. In order to improve the compatibility, a compound in which a fluorine atom is introduced into R which is an alkyl group is disclosed in JP-A-04-506817. The disclosed compound is a 2- or 3-ring compound having a cyclohexyl group and a phenyl group at the terminal, for example, a compound represented by the following formula (6), which has a single bond as a bonding group in the central part of the molecule. However, it does not have other linking groups, such as the 1,2-ethylene group. Further, the substituents on the terminal phenyl group are limited to fluorine atoms, and do not teach or suggest other substituents such as fluoroalkyl groups and fluoroalkoxy groups.

[0012]

[Chemical 11]

However, such a compound does not improve the compatibility at all, and in particular, the compound of the formula (6) does not show even a liquid crystal phase. A compound having such a large Δε and good compatibility is not known yet, and therefore, a large Δ
When a liquid crystalline compound having ε is used as a composition component, the mixing ratio cannot be increased, and
At present, the size of the ε value is limited. Therefore, it is expected that a liquid crystal compound having a high specific resistance value and a large Δε and excellent compatibility with the existing liquid crystal compound will appear.

[0014]

The object of the present invention is to solve the above-mentioned drawbacks of the prior art, have a large Δε value, be electrically and chemically stable, and be compatible with existing liquid crystal compounds. With respect to the above, it is to provide a good liquid crystal compound, a liquid crystal composition containing the same, and a liquid crystal display device constituted by using the same.

[0015]

In order to achieve the above object, the invention claimed in the present application is as follows. (1) General formula (I)

[0016]

Embedded image _{F- (CH 2) n -E- (} CH 2 CH 2) k -G- (CH 2 CH 2) 1 -L- (CH 2 CH 2) m -Z-Q-Y (I) (In the formula, n is an integer of 1 to 10, k, l, and m are each independently an integer of 0 to 2, and the ring E is one or more hydrogen atoms on the 6-membered ring substituted with a fluorine atom. May have been 1,
4-cyclohexylene group or 1,4-phenylene group, G and L are each independently a covalent bond or one or more hydrogen atoms on the 6-membered ring may be substituted with a fluorine atom, 1, 4-cyclohexylene group or 1,4
-A phenylene group is shown, but when it is a covalent bond, G is preferred, ring Z is a 1,4-phenylene group which may be fluorine-substituted, and Q is a covalent bond or -O-.
Y is a fluoroalkyl group having 1 to 3 carbon atoms or a fluorine atom. However, when ring E is a 1,4-cyclohexylene group and at least one of G and L is a covalent bond, k + l + m ≠ 0, and when Q is —O—, Y is a fluorine atom. There is no such thing. )). (2) The liquid crystalline compound according to (1), wherein k, l and m are each independently 0 or 1, and the ring E is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. (3) k, l, m are each independently 0 or 1, and ring E is a 1,4-cyclohexylene group (1)
The liquid crystal compound according to item 1. (4) k is 1, l and m are 0, G is a covalent bond, and L is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group (3) The liquid crystal compound according to item 1. (5) L is a 1,4-cyclohexylene group (4)
The liquid crystal compound according to item 1. (6) The liquid crystal compound according to (4), wherein L is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. (7) k and l are 0, m is 1, G is a covalent bond, L is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. Liquid crystalline compounds. (8) L is a 1,4-cyclohexylene group (7)
The liquid crystal compound according to item 1. (9) The liquid crystalline compound according to (7), wherein L is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. (10) k and m are 1, l is 0, G is a covalent bond, L
Is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group, (3). (11) The liquid crystal compound according to (3), wherein k is 1, l and m are 0, and G and L are covalent bonds. (12) The liquid crystalline compound according to (1), wherein G and L are each independently a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. (13) A liquid crystal composition comprising at least one kind of the liquid crystalline compound described in (1) to (12). (14) As a first component, at least one kind of the liquid crystalline compound according to any one of (1) to (12) is contained, and as a second component, general formulas (II), (III) and (IV) are included.

[0017]

[Chemical 13]

(Where R is₁Is alkyl having 1 to 10 carbons
Group, V is F, Cl, CF₃, OCF₃, OCF₂
H or an alkyl group having 1 to 10 carbon atoms, L₁, L
₂, L ₃, L_FourEach independently represent H or F,
Z₁, Z₂Are each independently-(CH₂)₂-, -CH
═CH— or a covalent bond, and ring A is trans-14
Represents a cyclohexylene group or a 1,4-phenylene group
, A represents 1 or 2, and b represents 0 or 1. )
Containing at least one compound selected from the group consisting of
A liquid crystal composition having: (15) Any of (1) to (12) as the first component
Containing at least one liquid crystal compound according to
Two components are represented by the general formulas (V), (VI), (VII), (VII
I) and (IX)

[0019]

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(Where R is₂Is F, al having 1 to 10 carbon atoms
A kill group or an alkenyl group having 2 to 10 carbon atoms is shown. I
Even if there is a gap, any methylene group (-CH₂
-) May be substituted by an oxygen atom (-O-)
However, two or more methylene groups are continuously replaced by oxygen atoms.
It will not be done. Z₃Is-(CH₂)₂-,-COO
Or covalent bond, L_FiveAnd L₆Are each independent
Indicates H or F, and D ₁Is trans-1,4-cyclo
Hexylene group, 1,4-phenylene group or 1,3-di
Oxane-2,5-diyl group, and ring U is trans-
1,4-cyclohexylene group or 1,4-phenylene
Group, c and d each independently represent 0 or 1.
You )

[0021]

[Chemical 15]

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms, L ₇ represents H or F, and e represents 0 or 1.)

[0023]

Embedded image

(In the formula, R ₄ represents an alkyl group having 1 to 10 carbon atoms, I represents a trans-1,4-cyclohexylene group or 1,4-phenylene group, and L ₈ and L ₉ respectively represent Independently representing H or F, Z ₄ represents —COO— or a covalent bond, and Z ₅ represents —COO— or —C≡C.
Represents-, and f and g each independently represent 0 or 1. )

[0025]

[Chemical 17]

(In the formula, R ₅ and R ₆ each independently represent an alkyl group, an alkoxy group or an alkoxymethyl group having 1 to 10 carbon atoms, W is a trans-1,4-cyclohexylene group, 1,4 -Phenylene group or 1,3-pyrimidine-2,5-diyl group, K is trans-1,
A 4-cyclohexylene group or a 1,4-phenylene group is shown, and Z ₆ is -C≡C-, -COO-,-(CH ₂ ) _2-.
Or indicates a covalent bond)

[0027]

Embedded image

[0028] (wherein, R ₇ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, R ₈ is optional methylene group (-CH ₂ of .R ₈ represents an alkyl group having 1 to 10 carbon atoms
-) May be substituted by an oxygen atom (-O-), but two or more methylene groups are not continuously substituted by an oxygen atom. M represents a trans-1,4-cyclohexylene group or a 1,3-pyrimidine-2,5-diyl group, and the rings N and P are each independently trans-.
1,4-cyclohexylene group or 1,4-phenylene group is shown, Z ₇ is —COO—, — (CH ₂ ) ₂ —, —CH
═CH— or a co-bond, Z ₈ is —C≡C—, —C
OO- or a covalent bond is shown, h is 0 or 1, and L ₁₀ is H or F. And a liquid crystal composition containing at least one compound selected from the group consisting of: (16) At least one liquid crystal compound according to any one of (1) to (12) is contained as a first component, and as a part of the second component, one of the general formulas (II), (III) and (IV ) At least one compound selected from the group consisting of
And containing at least one compound selected from the group consisting of the general formulas (V), (VI), (VII), (VIII) and (IX) as the other part of the second component. A characteristic liquid crystal composition. (17) A liquid crystal display device constituted by using the liquid crystal composition according to any one of (13) to (16).

The liquid crystalline compound represented by the general formula (I) of the present invention is selected from the group consisting of a fluorine atom, a fluoroalkyl group having 1 to 3 carbon atoms and a fluoroalkoxy group on the phenyl group which is one of the terminal rings. 2 to 4 ring structure having a fluorine atom-containing group on the other terminal ring, and in the case of 2 to 3 ring structure, at least one 1,2- It is characterized in that an ethylene or 1,4-butylene bonding group is introduced. By having such a structure, the compound (I) of the present invention
In addition to having a large Δε and good compatibility, each of them has a low viscosity and a high stability, that is, a high specific resistance value, and most of them have a wide liquid crystal temperature range. Therefore, when these compounds of the present invention are used as a component of a liquid crystal composition, a new liquid crystal composition having preferable properties can be provided.

The liquid crystalline compounds represented by the general formula (I) of the present invention have excellent properties as described above,
Among these, particularly, the following formulas (1-1) to (1-25)
The compound represented by is preferable because it has a large compatibility with Δε. In each formula, Q and Y have the same meanings as described above, and T ₁
To T ₈ are independently H or F, S ₁ is (CH ₂ CH ₂ ) _k , S ₂ is (CH ₂ CH ₂ ) _l , and S ₃ is (CH ₂ CH ₂ ) _m , k and l. , M have the same meanings as described above.

[0031]

[Chemical 19]

[0032]

Embedded image

[0033]

[Chemical 21]

Among these, two-ring system formula (1-1),
The compounds represented by (1-2) and (1-17) have excellent properties such that they are extremely compatible and have low viscosity, and in particular, the compounds represented by the formula (1-1) in which two rings are both phenyl groups ) And (1-2) have a feature that Δn is also large. Therefore, it is effective that these bicyclic compounds are used as a component of a composition that requires low viscosity.

Since the tricyclic compounds (1-3) to (1-16) and the tetracyclic compounds (1-18) to (1-25) both have high clearing points, they have the effect of widening the liquid crystal temperature range. . In addition to this, among the three-ring compounds, compounds having an ethylene bond between the rings have good compatibility, so that the TFT system used in applications for which such characteristics are expected, such as televisions for automobiles, is expected. It is effective as a component of a liquid crystal composition used in the liquid crystal display element. Further, the tetracyclic compound has the effect of greatly increasing the upper limit of the clearing point of the composition containing it, even if used in a small amount. When using them, a straight ring having a covalent bond between the rings is used for a composition requiring low viscosity, while a composition having a wider liquid crystal temperature range is required for the composition. Further, it is preferable to use one having an ethylene bond between the rings, which has excellent compatibility.

Among the substituents Q--Y, those having particularly excellent characteristics are CF ₃ , OCF ₃ , --OCF ₂ H, OCF ₂ C.
FHCF _3, a -CF ₂ CF ₂ H or F. However, when the substituent is F, it has the property of increasing Δε, so that in the 1,4-phenylene group Z,
F other than F may be substituted at the 3-position or substituted at the 3-position and the 5-position. The liquid crystal compound in which the substituent Q-Y is other than F, that is, a fluoroalkyl group or a fluoroalkoxy group having 1 to 3 carbon atoms exhibits particularly large Δε. At that time, especially Q-Y is -CF
_The compound of ₃ has a very large Δε and Q−Y is −
The compound that is OCF ₃ exhibits low viscosity with a large Δε, and Q-Y has —OCF ₂ CFHCF ₃ or —.
The compound which is OCF ₂ CF ₂ H exhibits a particularly large Δn together with a large Δε. That is, a compound having desired characteristics can be obtained by variously changing Q-Y according to the above.

When a larger Δε value is required, a fluorine atom may be introduced into the rings E, G, L and Z. Further, when a larger Δn is required, a compound containing more phenyl groups may be selected. The compound represented by the general formula (I) of the present invention can be effectively synthesized by a known method, for example, the method shown below.

"Introduction of Q-Y group" In the following description,
In the formula, T ₁ and T ₂ have the same meanings as described above, r ₁ is 0 to 2, r ₀ , r ₂ and r ₃ are integers of 0 to 1, respectively. When Q-Y is a perfluoroalkoxy group: This can be prepared by a known method, for example, as described in "JP-A-4-501575.
It can be synthesized according to the method of reacting carbon tetrachloride and HF with phenols as described in "Pages 7 to 9".

[0039]

[Chemical formula 22]

When Q-Y is a perfluoroalkyl group:
This is obtained by reacting copper powder with a perfluoroalkyl halide as an example of a perfluoroalkylating agent in an aprotic solvent by a known method, for example, as described in "4th Edition Experimental Chemistry Course, page 19.403". Then, it can be synthesized according to the method in which the solution of the CF ₃ .Cu complex generated here is reacted with an iodobenzene derivative.

[0041]

[Chemical formula 23]

[4th Edition Experimental Chemistry Course 19.39]
Carboxylic acid as described in "Page 0"._Fourso
Suitable results can also be obtained by processing. In addition,
As the fluoroalkylating agent, other than the above, CF₃CO
₂Na, FO₂SCF₂CO ₂Me, n-Bu_FourN⁺H
₂F₃ ^-, CF₃SiMe₃, CF₂Br₂Is also suitable
Can be used for

[0043]

[Chemical formula 24]

When Q-Y is a fluoroalkoxy group containing a hydrogen atom: This compound can be suitably synthesized by a known method, for example, by using an unsaturated fluoroalkene. For example, hexafluoropropene or tetrafluoroethylene can be used to construct a fluoroalkoxy moiety containing a hydrogen atom as follows.

[0045]

[Chemical 25]

It can also be synthesized by carrying out an etherification reaction under basic conditions using a fluoroalkyl halide such as fluoroalkyl iodide.

[0047]

[Chemical formula 26]

When Q-Y is a fluoroalkyl group containing a hydrogen atom: This can be used, for example, as a benzaldehyde derivative as described in "JOC, 40,578 (1975)". After treatment with sulfur trifluoride (DAST) or sonication in the presence of fluoroalkyl iodide and zinc as described in "Synthetic Organic Chemistry Vol. 41 No. 5, p. 53". It can be synthesized by treating with DAST or by reacting a fluoroalkyl iodide with a phenyllithium derivative which is a known method.

[0049]

[Chemical 27]

[Synthesis of Compound of the Present Invention] Q-Y
A compound of the present invention, for example, a compound of the formula (1-
Representative compounds shown in 1) to (1-25) can be synthesized. Hereinafter, first, a method for synthesizing a 2-3 ring compound will be described.

Compound of the formula (1-1): First, both ends are protected with a hydroxyl group and a hydroxyl group of a normal alkane derivative substituted with halogen such as bromine, and this and magnesium are ether or tetrahydrofuran (hereinafter abbreviated as THF). Etc. in an aprotic solvent such as -50 ° C. to room temperature to obtain a Grignard reagent, to which a bromobenzene derivative (6) is allowed to act in the presence of a catalyst such as nickel acetylacetonate, and then deprotected. Thus, the alcohol derivative (7) is synthesized. The derivative (7) is allowed to act on DAST in a solvent such as chloroform or dichloromethane at -50 ° C to the boiling point of the solvent to synthesize a fluoroalkyl derivative (8). An alkyllithium such as butyllithium is allowed to act on this derivative (8) in THF at −50 ° C. to room temperature to prepare a compound (9). However, when the benzene derivative (6) as the raw material is bromobenzene, the lithiation reaction from the compound (8) to the compound (9) does not proceed properly, so that the compound (8) is treated with a catalyst such as aluminum chloride. In the presence of bromine, 4- (ω
Compound (9) is preferably obtained by synthesizing -fluoroalkyl) bromobenzene and lithiation thereof. The compound (9) thus obtained is reacted with zinc chloride in THF at −50 ° C. to room temperature to synthesize the compound (10). Tetrakistriphenylphosphine palladium was added as a catalyst to a THF solution of this compound (10), then the bromobenzene derivative (11) was added dropwise, the mixture was stirred or refluxed at room temperature, and then recrystallized to give the compound (1-1). Can be synthesized.

[0052]

[Chemical 28]

Compound of formula (1-2): First, the Grignard reagent (hereinafter abbreviated as (11) -Mg) obtained by using the bromobenzene derivative (11) as a raw material is aprotic solvent such as ether or THF. Medium, prepared at −50 ° C. to room temperature, to which ethylene oxide was added dropwise at that temperature,
A phenethyl alcohol derivative (12) is obtained. This derivative (12) is reacted with a brominating reagent such as HBr or tribromophosphine to synthesize a phenethyl bromide derivative (13). On the other hand, the compound (9) was reacted with iodine in THF to synthesize the compound (14), which was prepared from the phenethyl bromide derivative (13) as a raw material and was used as an aprotic solvent such as ether or THF. In addition to the Grignard reagent (13) -Mg prepared in the above, the compound (1-2) can be synthesized by allowing it to act at −50 ° C. to room temperature in the presence of a catalyst such as nickel acetylacetonate.

[0054]

[Chemical 29]

Compounds of formula (1-3) or (1-5):
Bromine in THF is allowed to act on the compound (9) to synthesize the compound (15). However, when synthesizing 4- (ω-fluoroalkyl) bromobenzene, as described above, the fluoroalkyl derivative (8) is brominated in the presence of a catalyst such as aluminum chloride to give the compound (1
5) should be obtained. Then, a Grignard reagent of the compound (15) thus obtained is prepared, and cyclohexanedione monoethylene ketal is added thereto in THF at 0 ° C. to
It is allowed to act at room temperature to synthesize an alcohol derivative (17). An ion-exchange resin or an organic acid such as paratoluenesulfonic acid is allowed to act on the compound (17) to cause a dehydration reaction to synthesize a cyclohexene derivative (18). This derivative (18) is subjected to catalytic hydrogenation in the presence of a heterogeneous catalyst such as Pd / C or Raney nickel to give compound (19)
To synthesize. The protecting group of this compound (19) is removed by reacting it with an acid, and thus the compound (2
0) to Grignard reagent (11) -Mg or (13) prepared in an aprotic solvent such as ether or THF.
-Mg, and then from the above compound (17) (1
Dehydration and catalytic hydrogenation are carried out in the same manner as in the reaction of 9), and then purification operations such as recrystallization are carried out to give the compound (1-
3) or (1-5) can be obtained.

[0056]

Embedded image

Compounds of formula (1-4) or (1-9):
The phenethyl bromide derivative (22) is synthesized in the same manner as in the step of obtaining the compound (1-2) except that the compound (11) is replaced with the compound (15). Then, the compound (1-4) or (1-9) is prepared in the same manner as in the step of obtaining the compound (1-3) or (1-5) except that the derivative (22) is used instead of the compound (15). Can be obtained.

[0058]

[Chemical 31]

Compound of formula (1-6): Tetrakistriphenylphosphine palladium is added as a catalyst to a THF solution of the above-mentioned compound (10), and then the bromobenzene derivative (6) is added dropwise, followed by stirring or refluxing at room temperature. The compound (26) is obtained. Compound (8) with compound (26)
Compound (1-6) can be obtained in the same manner as in the step of obtaining compound (1-1) except for substituting

[0060]

Embedded image

Compound of formula (1-7): The Grignard reagent obtained by using the bromobenzene derivative (6) as a raw material is treated with -50 in an aprotic solvent such as ether or THF.
It is prepared at ℃ to room temperature, and ethylene oxide is added dropwise thereto at that temperature to obtain a phenethyl alcohol derivative (29). This derivative (29) is reacted with a brominating reagent such as HBr or tribromophosphine to give a phenethyl bromide derivative (30), and this Grignard reagent is treated in an aprotic solvent such as ether or THF at -50 ° C to room temperature. It is prepared under the following conditions, and the compound (15) is allowed to act on it in the presence of a catalyst such as nickel acetylacetonate to obtain the compound (31). Compound (1-7) can be obtained in the same manner as in the step of obtaining compound (1-1) except that compound (31) is used instead of compound (8).

[0062]

[Chemical 33]

Compound of formula (1-8) or (1-10): The compound (27) or (32) is reacted with bromine in THF, or the compound (26) or (31) is used.
Compound (33) or (34) is synthesized by reacting bromine with bromine in the presence of a catalyst such as aluminum chloride.
The Grignard reagent of the compound (13) prepared at ℃ to room temperature is allowed to act in the presence of a catalyst such as nickel acetylacetonate to give the compound (1-8) or (1-10)
Get.

[0064]

Embedded image

Compound of formula (1-11): 4- (2- (4
Compound (35) obtained from -oxocyclohexyl) ethyl) cyclohexanone is subjected to Wittig reaction using a suitable phosphonium salt to synthesize compound (36), which is a heterogeneous catalyst such as Raney nickel or Pd / C. Hydrogenation in the presence of gives compound (37). Compound (1) except that compound (24) is replaced with compound (37)
-4) in the same manner as in the step of obtaining compound (1-1)
1) can be obtained.

[0066]

Embedded image

Compound of formula (1-12): Compound (3)
Compound (1-1) except that 5) is replaced with compound (16).
Compound (39) was synthesized in the same manner as in the step of obtaining 1), and the Grignard reagent of compound (30) prepared above was prepared in an aprotic solvent such as ether or THF at −50 ° C. to room temperature. The mixture is allowed to act at that temperature, and then dehydration reaction and hydrogenation are sequentially performed to synthesize the compound (40). Compound (1) is obtained in the same manner as in the case of obtaining compound (1-1) except that compound (8) is replaced with compound (40).
-12) can be obtained.

[0068]

Embedded image

Compound of formula (1-13): Compound (3)
Compound (1-1) except that 5) is replaced with compound (42).
Compound (43) is synthesized in the same manner as in the step of obtaining 1), and compound (43) is synthesized in the same manner as in the step of obtaining compound (1-5) except that compound (20) is replaced with compound (43). 1-13) can be obtained.

[0070]

Embedded image

Compound of formula (1-14): The cyclohexanone derivative (39) was added with the Grignard reagent of the compound (6) prepared at -50 ° C to room temperature in an aprotic solvent such as ether or THF. The compound (44) is allowed to act at temperature, and then dehydration reaction and hydrogenation are carried out in order.
To synthesize. An alkyllithium such as butyllithium is allowed to act on this in THF at −50 ° C. to room temperature to prepare a compound (45). Then, this is reacted with bromine in THF to obtain a compound (46). However, compound (44)
When 1 is 1-fluoroalkyl-4-phenylcyclohexane, it is preferable to synthesize it with bromine in the presence of a catalyst such as aluminum chloride to synthesize the compound (46). Compound (1-14) can be obtained in the same manner as in the step of obtaining compound (1-8) except that compound (33) is replaced with compound (46).

[0072]

[Chemical 38]

Compound of formula (1-15): Compound (2)
Compound (1-15) can be obtained in the same manner as in the step of obtaining compound (1-5) except that 0) is replaced with the cyclohexanone derivative (38).

[0074]

[Chemical Formula 39]

Compound of formula (1-16): Compound (4)
Bromine is allowed to act on 1) in THF, or the compound (40) is brominated in the presence of a catalyst such as aluminum chloride to synthesize the compound (47). Compound (1-16) can be obtained in the same manner as in the step of obtaining (1-10) except that compound (33) is replaced with compound (47).

[0076]

[Chemical 40]

Compound of formula (1-17): Compound (2)
Compound (1-17) can be obtained in the same manner as in the step of obtaining compound (1-5) except that 0) is replaced with cyclohexanone derivative (39).

[0078]

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Next, a method for synthesizing a 4-ring compound will be shown. In the following description, the compounds (44), (40),
A compound obtained by reacting (26) or (31) with a lithiation reagent such as alkyllithium in THF, or with bromine using aluminum chloride or the like as a catalyst, and then with a lithiation reagent. (45), (41), (27) or (32) is Ar
-Li, the cyclohexane derivative (43), (3
8), (20) or (25) are collectively referred to as R = O.

Formulas (1-19) to (1-21) or (1
-24) Compound: First, these Ar-Li or R
= O as a starting material, a 4-ring precursor compound (49) (5
0), (51) or (52) is synthesized. That is,
Zinc chloride in THF is allowed to act on Ar-Li at -50 ° C to room temperature to synthesize a compound (48).
After tetrakistriphenylphosphine palladium is added to the solution as a catalyst, the bromobenzene derivative (6) is added dropwise and stirred or refluxed at room temperature to synthesize the compound (49).

Further, in the cyclohexanone derivative R = O,
Compound (50) is synthesized by reacting the Grignard reagent of compound (6) prepared in an aprotic solvent such as ether or THF at −50 ° C. to room temperature, and then sequentially performing dehydration reaction and hydrogenation. Further, the Grignard reagent of the compound (30) prepared at −50 ° C. to room temperature in an aprotic solvent such as ether or THF is added to Ar—Li,
The compound (51) is synthesized by acting in the presence of a catalyst such as nickel acetylacetonate.

Further, in the cyclohexanone derivative R = O,
In an aprotic solvent such as ether or THF, -50 ° C
The Grignard reagent of the compound (30) prepared at room temperature is allowed to act, and then dehydration reaction and hydrogenation are sequentially performed to synthesize the compound (52). The precursor compounds (49) to (52) obtained above are treated with an alkyllithium such as butyllithium in THF to give the compound (5
3) or by reacting bromine in a halogen-based solvent such as methylene chloride with aluminum chloride as a catalyst to synthesize compound (55), which is treated with alkyllithium such as butyllithium in THF. Compound (56) is synthesized. Compound (9) with compound (53)
Alternatively, the compound of (1-19) to (1-21) or (1-24) (when m = 0) is obtained in the same manner as in the step of obtaining the compound (1-1) except that it is replaced with (56). Can be synthesized.

By reacting the above compound (53) with bromine in THF, (54) can be synthesized. This compound (54) or the above compound (55)
The phenethyl bromide derivative (13) is allowed to act in an aprotic solvent such as ether or THF at −50 ° C. to room temperature and in the presence of a catalyst such as nickel acetylacetonate to give (1-19) to (1- 21) or (1-24)
The compound (when m = 1) can be synthesized.

[0084]

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Formulas (1-18), (1-12), (1-2)
3) or the compound of (1-25): First, Ar-
Cyclohexanone derivatives (58), (63), which are 4-ring precursor compounds, starting from Li or R = O
(68) or (73) is synthesized. That is, Ar-
The cyclohexanedione monoethylene ketal (16) is allowed to act on Li at −50 ° C. to room temperature in an aprotic solvent such as ether or THF, and then dehydrated by an acid, and hydrogen is used with Raney nickel or Pd / C as a catalyst. Compound (57) is synthesized by addition treatment. The protecting group of this compound (57) is removed with an acid to obtain a cyclohexanone derivative (58).

A compound (60) was synthesized by reacting R = O with a Grignard reagent of 4-methoxybromobenzene (59), followed by dehydration with an acid and catalytic hydrogenation treatment using Pd / C as a catalyst. To do. This compound (6
0) is refluxed in toluene or xylene in the presence of an acid catalyst to obtain a phenol derivative (61).
Nuclear hydrogenation is carried out in the presence of a d / C catalyst to obtain a cyclohexanol derivative (62). In addition, in this reaction, even when R contains a phenyl group, the benzene ring having a hydroxyl group bonded thereto is almost selectively hydrogenated. The cyclohexanol derivative (62) is oxidized with an oxidizing agent to synthesize a cyclohexanone derivative (63).

Further, by reacting Ar-Li with ethylene oxide, a compound (64) was obtained, which was converted into HB
Compound (65) by bromination with r or tribromophosphine
Get. Then, the Grignard reagent (66) of this product is reacted with the compound (16) to obtain the compound (67), and the protecting group of this product is removed with an acid to obtain the cyclohexanone derivative (68).

Furthermore, the compound (69) is obtained by reacting ethylene oxide with the Grignard reagent of 4-methoxybromobenzene (59) and then brominating with HBr or tribromophosphine. The cyclohexanone derivative (73) can be synthesized in the same manner as the reaction for synthesizing the compound (63) except that the compound (59) is replaced with the compound (69).

A precursor compound (58) obtained as described above,
In (63), (68) or (73), the compound (1
1) or (13), the Grignard reagent is allowed to act, dehydration with an acid and catalytic hydrogenation treatment using Raney nickel, Pd / C or the like as a catalyst are sequentially performed, and a compound (1-18),
(1-22), (1-23) or (1-25) can be synthesized.

[0090]

[Chemical 43]

However, in the liquid crystalline compound represented by the general formula (I) of the present invention, Q-Y is CF ₂ H or CF ₂ CF.
₂ H, CF ₂ CFHCF ₃ , OCF ₂ H, OCF ₂ CF
In the case of HCF ₃ or OCF ₂ CF ₂ CF ₂ H, it is preferable to introduce a ring ZQY site by the following route, separately from the above.

[0092]

[Chemical 44]

The liquid crystal composition provided by the present invention may include only the first component containing at least one liquid crystalline compound represented by the general formula (I), but in addition to this, the second component as described above may be used. At least one compound selected from the group consisting of general formulas (II), (III) and (IV) (hereinafter referred to as the second component A) and / or general formulas (V) and (V
A mixture of at least one compound selected from the group consisting of I), (VII), (VIII) and (IX) (hereinafter referred to as the second component B) is preferable, and further, a threshold voltage, a liquid crystal phase A known compound may be mixed as a third component for the purpose of adjusting the temperature range, Δn, Δε, viscosity and the like.

Among the above-mentioned second component A, suitable examples of the compound contained in the general formula (II) are the following (2-1) to (2-1).
5), (3-1) to (3-48) as preferable examples of the compound contained in the general formula (III), and (4-1) to (4-) as preferable examples of the compound contained in the general formula (IV). 41) can be mentioned respectively.

[0095]

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[0096]

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[0097]

[Chemical 47]

[0098]

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[0099]

[Chemical 49]

[0100]

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[0101]

[Chemical 51]

[0102]

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[0103]

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[0104]

[Chemical 54]

The compounds represented by the general formulas (II) to (IV) have a positive Δε and are very excellent in thermal stability and chemical stability. The amount of the compound used is appropriately in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40 to 95% by weight.

Next, among the second component B, preferred examples of the compounds contained in the general formulas (V), (VI) and (VII) are (5-1) to (5-27) and (5-27), respectively. 6-
1) to (6-3) and (7-1) to (7-13).

[0107]

[Chemical 55]

[0108]

[Chemical 56]

[0109]

[Chemical 57]

[0110]

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[0111]

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The compounds represented by the general formulas (V) to (VII) have a positive Δε and a large value, and are used as a component of the composition for the purpose of particularly reducing the threshold voltage. It is also used for the purpose of adjusting viscosity, adjusting Δn and widening the temperature range of the liquid crystal phase, and for improving steepness. Further, among the second component B, preferred examples of the compounds contained in the general formulas (VIII) and (IX) are (8
-1) to (8-15) and (9-1) to (9-14)
Can be mentioned.

[0113]

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[0114]

[Chemical formula 61]

[0115]

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[0116]

[Chemical formula 63]

The compounds represented by the general formulas (VIII) and (IX) are compounds in which Δε is negative or weakly positive. Among them, the compound represented by the general formula (VIII) is mainly used as a composition component. The compound represented by the general formula (IX) is used for the purpose of decreasing the viscosity and adjusting Δn, and for the purpose of widening the temperature range of the liquid crystal phase and / or adjusting Δn.

The compounds represented by the above general formulas (V) to (IX) are indispensable compounds especially when preparing a liquid crystal composition for STN type display system or ordinary TN type display system. The amount of the compound used depends on the usual STN type display system or T
When preparing a liquid crystal composition for the N-type display system, a range of 1 to 99% by weight is suitable for the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40% by weight.
Is in the range of up to 95% by weight.

The liquid crystal composition provided according to the present invention exhibits excellent characteristics when it contains at least one liquid crystal compound represented by the general formula (I) in a proportion of 0.1 to 99% by weight. It is preferable because it is apt. The liquid crystal composition is generally prepared by a method known per se, for example, a method in which various components are mutually dissolved at high temperature. Further, if necessary, appropriate additives are added to improve and optimize according to the intended use. Such additives are well known to those skilled in the art, and are described in detail in the literature and the like. Usually, a chiral dopant or the like having an effect of inducing a helical structure of liquid crystal to adjust a necessary twist angle and preventing reverse twist is added.

If a dichroic dye such as a merocyanine-based, styryl-based, azo-based, azomethine-based, azoxy-based, quinophthalone-based, anthraquinone-based or tetrazine-based dye is added, it can be used as a GH-type liquid crystal composition. You can also The composition according to the present invention is an NCAP produced by encapsulating nematic liquid crystal in a microcapsule, or a polymer dispersed liquid crystal display device (PDLCD) produced by forming a three-dimensional network polymer in the liquid crystal, for example, a polymer network liquid crystal display device. (PNLCD) and birefringence control (EC
It can also be used as a liquid crystal composition for B) type and DS type.

The following can be shown as examples of liquid crystal compositions containing the compound of the present invention. Compound N
o. Is the same as that shown in the examples below. Also, all the double bonds in 1,4-cyclohexylene and the alkyl chain are in the trans form.

Composition Example 1

[Chemical 64]

Composition Example 2

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Composition Example 3

[Chemical formula 66]

Composition Example 4

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Composition Example 5

[Chemical 68]

Composition Example 6

[Chemical 69]

Composition Example 7

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Composition Example 8

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Composition Example 9

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Composition Example 10

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Composition Example 11

[Chemical 74]

Composition Example 12

[Chemical 75]

Composition Example 13

[Chemical 76]

Composition Example 14

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Composition Example 15

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Composition Example 16

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Composition Example 17

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Composition Example 18

[Chemical 81]

Composition Example 19

[Chemical formula 82]

The clearing point of this product was 113.8 ° C., the threshold at a cell thickness of 8.7 μm was 2.59 V, and Δε was 4.
5, Δn is 0.090, and the viscosity at 20 ° C. is 23.1.
It was mPa · S.

Composition Example 20

[Chemical 83]

The clearing point of this product was 92.1 ° C., the threshold at the cell thickness of 8.7 μm was 1.78 V, and Δε was 9.1.
Δn is 0.093, viscosity at 20 ° C is 31.2 mP
It was aS.

Composition Example 21

[Chemical 84]

The clearing point of this product was 89.5 ° C., the threshold value was 2.09 V, and Δε was 5.5 at a cell thickness of 8.7 μm.
Δn is 0.128, viscosity at 20 ° C is 22.7 mP
It was aS.

Composition Example 22

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The clearing point of this product was 76.1 ° C., the cell thickness was 8.7 μm, the threshold was 1.89 V, and Δε was 7.6.
Δn is 0.124, viscosity at 20 ° C is 18.4 mP
It was aS.

Composition Example 23

[Chemical 86]

The clearing point of this product was 77.0 ° C., the threshold at a cell thickness of 8.7 μm was 0.96 V, and Δε was 24.
2, Δn is 0.145, and the viscosity at 20 ° C. is 39.8.
It was mPa · S.

[0150]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples. In each example, C is a crystal, S is a smectic phase, N is a nematic phase, I is an isotropic liquid phase, and the unit of the phase transition point is ° C.

Example 1 1- (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3,5-difluoro-4- (3,5-
Difluoro-4-trifluoromethylphenyl) benzene (in the formula (1), n = 3, ring E = 1,4-cyclohexylene, G = covalent bond, L = ring Z = 3,5-difluoro-1,4 -Phenylene, k = 1, l = 0, m = 0,
A compound in which Q = covalent bond and Y = CF ₃ (No. 8)
0)) production

(First stage) 150 g (0.78 mol) of commercially available 3,5-difluorobromobenzene and 18.9 g (0.78 mol) of dried magnesium were added to ether 6
Prepare Grignard reagent in 00 ml and add -5
Under cooling at 0 ° C, 100 g of ethylene oxide (2.27 m
ol) in 100 ml ether solution was gradually added dropwise. After the dropping was completed, the reaction solution was warmed to room temperature and stirred for 1 hour.
It was added to 500 ml of 6N hydrochloric acid, and the product was extracted with toluene. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and then the solvent was evaporated. HBr water (47%) (500 ml) was added to the residue and the mixture was refluxed for 7 hours.
Then, vacuum distillation was performed using a Vigreux tube. Thus 2
B. Under Torr. 3,5-difluorophenethyl bromide, which is a colorless transparent liquid exhibiting a p.
g (0.19 mol) was obtained. The yield of this product from 3,5-difluorobromobenzene was 23.8%.
20.0 g of the 3,5-difluorophenethyl bromide
(90.5 mmol) and 2.2 g of dried magnesium
(90.5 mmol), a Grignard reagent was prepared in 150 ml of ether and then cooled to 0 ° C., and commercially available cyclohexanedione monoethylene ketal 1
4.2 g (90.9 mmol) of 130 ml ether solution was added dropwise. After completion of dropping, the reaction solution was warmed to room temperature and stirred for 3 hours. This reaction solution was added with 6N hydrochloric acid (500 ml)
In addition, the product was extracted with toluene, washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. To the remaining 20 g, 100 ml of toluene and 1 g of Amberlyst were added, and the mixture was refluxed for 5 hours while removing water produced by the reaction with Gene Stark. Then, 2 g of ethylene glycol was added and the mixture was refluxed for another 2 hours. 100 ml of water was added to the reaction solution, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. Toluene / ethyl acetate = 4 as the developing solvent
Purification by column chromatography using 1/1, and the purified product thus obtained is 5% Pd / C catalyst (1.
Hydrogenated in ethanol in the presence of 02 g). After completion of the reaction, the catalyst was filtered off and ethanol was distilled off under reduced pressure.
After refluxing the obtained concentrate in 80 ml of formic acid for 3 hours,
After adding 200 ml of water to this and extracting the product with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, the toluene layer was dried over magnesium sulfate, and the toluene was distilled off.
10.1 g (42.4 mmol) of (3,5-difluorophenylethyl) -1-cyclohexanone was obtained. The yield of this product from 3,5-difluorobromobenzene was 46.6%.

(Second stage) 3-fluorobromopropane 2
00.0 g (1.42 mol) was dissolved in 3 l of toluene, and 37.2 g (1.4
(2 mol) was added and the mixture was refluxed for 15 hours. The product is filtered off,
It was sucked and dried to obtain 486 g (1.21 mol) of 3-fluoropropyltriphenylphosphine bromide. Yield 85.2%.

(Third stage) 22.0 g (54.6 m) of the above 3-fluoropropyltriphenylphosphine bromide
mol) with 100 ml of THF, and under a nitrogen gas atmosphere-
Cooled to 50 ° C. A solution of 6.10 g (54.5 mmol) of potassium-t-butoxide in 70 ml of THF was added thereto, and the mixture was stirred for 3 hours. 4- (3,5-difluorophenethyl) -1- synthesized in the first step was added to this reaction solution.
Cyclohexanone 10.0 g (42.0 mmol) 8
0 ml of THF solution was added dropwise, and the temperature was kept as it was for 1 hour.
Then, the mixture was warmed to room temperature and stirred for 4 hours. 200 ml of water was added to the obtained reaction solution, the product was extracted with ethyl acetate, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure,
The residue was purified by column chromatography using toluene as a developing solvent. The purified product thus obtained is hydrogenated in ethanol in the presence of 5% Pd / C catalyst, the catalyst is filtered off after completion of the reaction, and ethanol is distilled off under reduced pressure to give 4- (3,5-difluorophenethyl). ) -1-
2.51-g of (3-fluoropropyl) cyclohexane
(8.83 mmol) was obtained. Yield 21.0%.

(Fourth stage) 2.51 g (8.83 mmol) of 4- (3,5-difluorophenethyl) -1- (3-fluoropropyl) cyclohexane was added to THF30.
ml was added, and it cooled at -50 degreeC under nitrogen gas atmosphere. To this, 7 ml (11.4 mmol) of a hexane solution of 1.63N normal butyl lithium was dropped by a syringe, and after stirring at the same temperature for 1 hour, 0.5 mol of zinc chloride TH was added.
22.8 ml (11.4 mmol) of F solution was added dropwise.
After completion of the dropping, the temperature of the reaction product is warmed to room temperature, and further 2
Stir for hours. After adding 250 mg of tetrakistriphenylphosphine palladium as a catalyst to this reaction solution,
2.97 g (11.4 mmol) of 3,5-difluoro-4-trifluoromethylphenyl bromide was added dropwise and 2
Reflux for hours. This reaction solution was added to cooled 6N hydrochloric acid,
The product was extracted with toluene, and the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and then the solvent was distilled off to obtain 8.5 g of an orange suspension. This was purified by column chromatography on silica gel using toluene / heptane = 1/1 as a developing solvent, and then recrystallized to give 1- (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3. , 5-difluoro-
0.35 g (0.75 g) of trans-form of 4- (3,5-difluoro-4-trifluoromethylphenyl) benzene
mmol) obtained. Yield 8.49%. C-I point 83.7
° C. 1H-NMR (CDCl3) δ (ppm): 7.1
0 (d, 2H), 6.84 (d, 2H), 4.69
(T, 1H), 4.16 (t, 1H), 2.66 (t,
2H), 1.84 to 0.88 (m, 18H).

Example 2 1- (2- (4- (4- (2-fluoroethyl) cyclo)
Hexyl) cyclohexyl) ethyl) -4-trifluoro
Romethoxybenzene (n = 2 in the formula (1), ring E =
1,4-cyclohexylene, G = covalent bond, L = 1,4
-Cyclohexylene, ring Z = 1,4-phenylene, k =
l = 0, m = 1, Q = -O-, Y = CF ₃The compound that is
(No. 17))

(First stage) 125 g (0.556 mol) of ethoxycarbonylmethyldimethylphosphonate was mixed with TH
What added F1l was cooled to -50 degreeC under nitrogen gas atmosphere, and potassium-t-butoxide 62.3g was added to this.
(0.556 mol) was gradually added, and the mixture was stirred at this temperature for 1 hour. Bicyclohexanedione monoethylene ketal 117 g (0.464 mol) THF40
After gradually adding 0 ml solution, the mixture was stirred at room temperature for 10 hours. 500 ml of water was added to this reaction solution, and the product was extracted with toluene. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and evaporated under reduced pressure to remove the solvent to obtain 218.2 g of a yellow liquid. This was dissolved in ethanol and hydrogenated in the presence of Raney nickel catalyst. After completion of the reaction, the catalyst was filtered off and ethanol was distilled off under reduced pressure. The residue was purified by column chromatography on silica gel using toluene as the developing solvent. A colorless oily 4- (1,4-dioxaspiro [4.5] decyl) cyclohexylmethanoic acid ethyl ester was added to
83.2 g (0.464 mol) was isolated.

(Second stage) lithium aluminum hydride 1
100 ml of dry THF to 7.6 g (0.464 mol)
Was cooled to 0 ° C., and the above 4- (1,
4-Dioxaspiro [4.5] decyl) cyclohexylmethanoic acid ethyl ester 183.2 g
A solution of (0.464 mol) in 800 ml of THF was added dropwise, and the mixture was stirred at 0 ° C. for 3 hours and then at room temperature for 2 hours.
The reaction mixture was washed successively with 3N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and water, the solvent was evaporated, and the residue was recrystallized to give 2- (4- (1,
Colorless crystals of 4-dioxaspiro [4.5] decyl) cyclohexyl) ethanol 50.6 g (0.179 mo)
1) was isolated. The yield from bicyclohexanedione monoethylene ketal was 38%.

(Third step) 20 g (70.8 mmol) of 2- (4- (1,4-dioxaspiro [4.5] decyl) cyclohexyl) ethanol above was added to 70 ml of dichloromethane.
After dissolving in ml, DAST 13g (80.7mm
ol) was added dropwise and the mixture was stirred at 0 ° C. for 1 hour. Water was added to this reaction solution, the resulting organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated. The residue was purified by column chromatography on silica gel using heptane / ethyl acetate = 5/1 as a developing solvent, and 1- (4- (1,4-dioxaspiro [4.5] decyl) cyclohexyl) -2-fluoro Got ethane. To this, 80 ml of formic acid was added and refluxed for 2 hours, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated to give 4- (4- (2
8.0 g (35.3 mmol) of -fluoroethyl) cyclohexyl) cyclohexanone were isolated. 2- (4-
The yield from (1,4-dioxaspiro [4.5] decyl) cyclohexyl) ethanol was 49.9%.

(Fourth stage) A Grignard reagent prepared from 54 g (220 mmol) of 4-trifluoromethoxybromobenzene and 5.4 g (220 mmol) of dried magnesium in a 250 ml ether solvent was cooled to -50 ° C. Ethylene oxide 29.3g (670m
(mol) was gradually added dropwise. After completion of the dropwise addition, the reaction mixture was gradually warmed to room temperature and further stirred at room temperature for 1 hour. The reaction solution was added to 300 ml of 6N hydrochloric acid, the product was extracted with ethyl acetate, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. The residue was distilled under reduced pressure using a Vigreux tube.
Under 3.5 Torr b. 14.5 g (70.3 mmol) of 2- (4-trifluoromethoxyphenyl) ethanol, which is a colorless liquid exhibiting a p82 ° C to 84 ° C, was isolated.
To this, 60 ml of xylene and HBr water (47%) 6
0 ml was added and the mixture was refluxed for 9 hours. Water was added to the reaction mixture, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, the resulting organic layer was dried over magnesium sulfate, and the solvent was evaporated. The residue was distilled under reduced pressure using a Vigreux tube. B. Under 4 Torr. 12.0 g (51.9 mmol) of 2- (4-trifluoromethoxyphenyl) bromoethane, which is a colorless liquid showing p74 ° C., was isolated. The yield of this product from 4-trifluoromethoxybromobenzene was 23.6%.

(Fifth stage) 7.0 g (30.3 m) of 2- (4-trifluoromethoxyphenyl) bromoethane as described above
mol) and dried magnesium 0.74 g (30.4
(4 mmol) and the Grignard reagent prepared in 40 ml ether solvent were cooled to 0 ° C., and then 2.2 g (9.7 mmol) of 4- (4- (2-fluoroethyl) cyclohexyl) cyclohexanone synthesized in the third step. Of 3
0 ml ether solution was added dropwise, and the mixture was stirred at 0 ° C. for 3 hours.
To the reaction solution was added 6N hydrochloric acid, and the product was extracted with toluene. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. 100 ml of toluene and Amberlyst 5 were added to the obtained yellow oily substance.
00 mg was added, and the mixture was refluxed for 4 hours while removing water generated by the reaction with Gene Stark. The amberlyst was filtered off, the solvent was distilled off, and the residue was purified by column chromatography on silica gel using toluene as a developing solvent to give 4- (4- (2-fluoroethyl) cyclohexyl)-. 1.8 g (4.5 mmol) of 1- (2- (4-trifluoromethoxyphenyl) ethyl) -1-cyclohexene was isolated. 1.2 g (3.0 mmol) of this product was added to 5% Pd / C catalyst 0.
Hydrogenated in ethanol solution in the presence of 12 g. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. The residue is recrystallized to give a colorless 1- (2) which exhibits a smectic phase.
0.37 g (0.90) of only trans-form of-(4- (4- (2-fluoroethyl) cyclohexyl) cyclohexyl) ethyl) -4-trifluoromethoxybenzene
mmol) isolated. The yield of this product from 4- (4- (2-fluoroethyl) cyclohexyl) cyclohexanone was 9.3%. S _B -N point 68.8 ° C, NI point 103.5 ° C. 1H-NMR (CDCl3) delta (ppm): 7.19
(T, 4H), 4.74 (t, 1H), 4.21 (t,
1H), 2.58 (t, 2H), 1.82-0.99
(M, 26H).

Example 3 1- (4- (3-fluoropropyl) cyclohexyl)
-3,5-difluoro-4- (2- (3-fluoro-4
-Trifluoromethoxyphenyl) ethyl) benzene (n = 3 in the formula (1), ring E = 1,4-cyclohexylene, G = covalent bond, L = 3,5-difluoro-1,
4-phenylene, the manufacture of ring Z = 3- fluoro-1,4-phenylene, k = l = 0, m = 1, Q = -O-, Y = CF 3 , compound (No.122))

(First stage) A Grignard reagent prepared from 193.1 g (1.00 mol) of 3,5-difluorophenyl bromide and 24.3 g (1.00 mol) of dried magnesium in a THF solvent was cooled to 0 ° C. And then add cyclohexanedione monoethylene ketal 15
6 g (1.00 mol) of a 300 ml ether solution was added dropwise. After completion of dropping, the reaction solution was warmed to room temperature, stirred for 3 hours, added to 1 L of 6N hydrochloric acid, and the product was extracted with toluene. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. 8 g of Amberlyst and 1000 ml of toluene were added to the residue, and the mixture was refluxed for 7 hours while removing water produced by the reaction with Gene Stark. After removing the amberlyst in the reaction product by filtration, toluene was distilled off under reduced pressure. The residue was purified by column chromatography on silica gel using toluene as a developing solvent to obtain a cyclohexene derivative.
To 62 g of this cyclohexene derivative, 500 ml of formic acid was added and refluxed for 5 hours, then, 500 ml of water was added to the reaction solution,
The product was extracted with toluene. The toluene layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was distilled under reduced pressure to give 4-
(3,5-difluorophenyl) cyclohexanone 4
3.8 g (20.8 mmol) was obtained. Yield 20.8
%.

(Second stage) 3 synthesized in the second stage of Example 1
-Fluoropropyltriphenylphosphine bromide 1
THF (60 ml) was added to 0.3 g (25.5 mmol), and the mixture was cooled to -50 ° C under a nitrogen atmosphere. To this was added 2.86 g (25.5 mmol) of potassium t-butoxide 4
After adding 0 ml THF solution, the mixture was stirred at that temperature for 3 hours. 43.8 g (20. 20%) of 4- (3,5-difluorophenyl) cyclohexanone synthesized in the first step was added to this reaction solution.
(8 mmol) in 100 ml of THF was added dropwise, and the mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. 200 ml of water was added to the reaction solution, the product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The yellow solution obtained by distilling off the solvent was purified by column chromatography on silica gel using toluene as a developing solvent. The obtained cyclohexylidene derivative was hydrogenated in ethanol using Pd / C as a catalyst. After completion of the reaction, the catalyst was filtered off and ethanol was distilled off under reduced pressure. The product was recrystallized using a mixed solvent of heptane and ethanol to obtain 1.50 g (6.14 mmol) of 4- (3,5-difluorophenyl) -1- (3-fluoropropyl) cyclohexane. Yield 29.5%.

(Third step) 20 m of THF was added to 1.50 g (6.14 mmol) of 4- (3,5-difluorophenyl) -1- (3-fluoropropyl) cyclohexane.
The mixture to which 1 was added was cooled to −50 ° C. under a nitrogen atmosphere, and a hexane solution of 1.63N n-butyllithium 4 was added thereto.
ml (6.51 mmol) was added dropwise with a syringe, and the mixture was stirred at the same temperature for 1 hour. 1.6 Iodine was added to this reaction solution.
A solution of 5 g (6.51 mmol) in 10 ml of THF was added dropwise, and the mixture was stirred at the same temperature for 30 minutes. Add this reaction mixture to 6
In addition to N hydrochloric acid, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate. After the solvent was distilled off, the residue was purified by column chromatography on silica gel using heptane as a developing solvent, and 4- (3,5-difluorophenyl-4-iodo) -1- (3-fluoropropyl) was obtained. 2.12 g (5.73 mmol) of cyclohexane was obtained. Yield 93.3%.

(Fourth step) 3-fluoro-4-trifluoromethoxyphenyl bromide 200.0 g (772 mm)
ol) and dried magnesium 18.8g (774mm
Ol) and the Grignard reagent prepared in ether from the solution were cooled to -50 ° C under a nitrogen gas atmosphere, and 100 ml (2.27 mol) of ethylene oxide in 100 ml of ether was added dropwise thereto. After completion of dropping, the reaction solution was stirred at 0 ° C. for 2 hours, the reaction product was added to 6N hydrochloric acid, and the product was extracted with toluene. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate. After the solvent was distilled off, 300 ml of 47% hydrobromic acid and 300 ml of xylene were added to the residue, and the mixture was refluxed for 9 hours while removing water produced by the reaction with Gene Stark. Water 5 for reaction
00 ml was added, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated. The residue was distilled under reduced pressure to obtain 68.3 g (238 mmol) of 3-fluoro-4-trifluoromethoxyphenethyl bromide. Yield 30.7%.

(Fifth stage) 1.64 g (5.
71 mmol) and 0.14 g of dried magnesium
The Grignard reagent prepared in 10 ml of ether from (5.76 mmol) was cooled to 0 ° C., and 0.10 g (0.39 mm) of nickel acetylacetonate was added thereto.
was added, and then 2.12 g (5.73 mmo) of 4- (3,5-difluorophenyl-4-iodo) -1- (3-fluoropropyl) cyclohexane synthesized in the third step.
20 ml ether solution of l) was added dropwise. The reaction solution was stirred at 0 ° C. for 1 hour, warmed to room temperature and then stirred for 3 hours. Then, the obtained reaction solution was added to 6N hydrochloric acid, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate. After distilling off the solvent, the residue was purified by column chromatography on silica gel using toluene as a developing solvent, and then recrystallized using a mixed solvent of heptane and ethanol,
1- (4- (3-fluoropropyl) cyclohexyl)
-3,5-difluoro-4- (2- (3-fluoro-4
-Trifluoromethoxyphenyl) ethyl) benzene 3
20 mg (0.692 mmol) was obtained. Yield 12.0
%. 1H-NMR data well supported the structure.

Example 4 1- (4- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) -3,5-difluoro-4-
(3-fluoro-4-trifluoromethoxyphenyl)
Benzene (n = 3 in formula (1), ring E = G = 1,4
-Cyclohexylene, L = 3,5-difluoro-1,4
- phenylene, production of ring Z = 3- fluoro-1,4-phenylene, k = l = m = 0 , Q = -O-, Y = CF 3 , compound (No.240))

(First step) From 107.1 g (555 mmol) of 3,5-difluorophenyl bromide and 14.0 g (575 mmol) of dried magnesium, THF6 was added.
Grignard reagent prepared in 00 ml was added with 500 of bicyclohexanedione monopropylene ketal at room temperature.
A ml THF solution was added dropwise, and the mixture was stirred at the same temperature for 5 hours. The reaction solution was cooled to 0 ° C., saturated ammonium chloride was added thereto, the product was extracted with ethyl acetate, the extract solution was washed with water, the organic layer was dried with magnesium sulfate, and then the solvent was distilled off. This gave 158 g of yellow crystals. To this, 700 ml of toluene and 7.9 g of 5% paratoluenesulfonic acid were added, and the mixture was refluxed for 9 hours. Two hours before the end of the reflux, 37 g of propylene glycol and 8.3 g of 5% paratoluenesulfonic acid were added to the system. The reaction solution was washed successively with 6N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate. 169 g of the residue obtained by distilling off the solvent was added to toluene / ethyl acetate = 1/9
Was used as a developing solvent to purify by column chromatography on silica gel to obtain 114 g (327 mmol) of 4- (3,5-difluorophenyl) -3-cyclohexenyl-1-cyclohexanone propylene ketal. Yield 56.9%.

(Second stage) 114 g (327 mmo) of 4- (3,5-difluorophenyl) -3-cyclohexenyl-1-cyclohexanone propylene ketal as described above.
1) was hydrogenated in a mixed solvent of ethyl acetate and ethanol in the presence of 44.8 g of Raney nickel catalyst. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. 50.0 g (1.09 mol) of formic acid and 300 m of toluene in the residue
1 was added and the mixture was refluxed for 4 hours. Water was added to this reaction solution, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and then toluene was distilled off under reduced pressure. The residue was purified by column chromatography on silica gel using toluene as a developing solvent, and 4- (3,5
56.8 g (194 mmol) of -difluorophenyl) cyclohexyl-1-cyclohexanone were obtained. Yield 5
9.3%.

(Third stage) 3 synthesized in the second stage of Example 1
-Fluoropropyltriphenylphosphine bromide 3
250 ml of THF was added to 6.1 g (89.5 mmol), and the mixture was cooled to -50 ° C under a nitrogen gas atmosphere. 10.0 g (89.5 mmol) of potassium t-butoxide was added to this.
100 ml of THF solution was added and the mixture was stirred for 3 hours.
4- (3,5-difluorophenyl) cyclohexyl-1-cyclohexanone 2 synthesized in the second step in this reaction solution
0.0 g (68.9 mmol) of 200 ml THF solution was added dropwise, and the mixture was stirred at the same temperature for 1 hour, then warmed to room temperature and stirred for 4 hours. 1 l of water was added to this reaction solution, the product was extracted with toluene, the extract was washed with water, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Toluene was used as a developing solvent for the residue,
Purification by column chromatography on silica gel gave 12.99 g of a yellow solution. This is 5% Pd
In the presence of 1.20 g of / C catalyst, hydrogenation was carried out in ethanol. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off. The residue was purified by column chromatography on silica gel using toluene as a developing solvent, and 4- (3-fluoropropylcyclohexyl) cyclohexyl-3,5-
8.33 g (24.6 mmol) of difluorobenzene was obtained. Yield 35.7%.

(Fourth stage) THF was added to 8.10 g (23.9 mmol) of 4- (3-fluoropropylcyclohexyl) cyclohexyl-3,5-difluorobenzene as described above.
The mixture to which 80 ml was added was cooled to −50 ° C. under a nitrogen gas atmosphere, and 16.9 ml (28.7 mmol) of a hexane solution of 1.63N n-butyllithium was added dropwise thereto with a syringe, and the mixture was stirred for 1 hour at the same temperature. After that, an additional 0.5 molar zinc chloride THF solution 58.4 ml (29.2
mmol) was added dropwise. After completion of the dropping, the temperature of the reaction solution was warmed to room temperature and further stirred for 2 hours. 0.72 of tetrakistriphenylphosphine palladium was added to this reaction solution.
After adding g (622 mmol), 7.44 g (2-fluoro-4-trifluoromethoxyphenyl bromide
(8.7 mmol) was added dropwise and the mixture was refluxed for 2 hours. Cooled 6N hydrochloric acid was added to the reaction solution, the product was extracted with ethyl acetate, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the organic layer was dried over magnesium sulfate, and the solvent was evaporated. The residue (13.9 g) was purified by column chromatography on silica gel using heptane as a developing solvent, and then recrystallized using a mixed solvent of heptane and ethanol to give 1- (4- (4- (3-fluoro Propyl) cyclohexyl) cyclohexyl) -3,5-difluoro-4
1.31 g (2.54 mmol) of-(3-fluoro-4-trifluoromethoxyphenyl) benzene was obtained.
Yield 10.6%. C-N point 78.5 ° C, N-I point 22
4.5 ° C. 1 H-NMR (CDCl ₃ ) δ (ppm):
7.37 (t, 3H), 6.85 (d, 2H), 4.6
9 (t, 1H), 4.16 (t, 1H), 2.46
(M, 1H), 2.02-0.81 (m, 23H).

Example 5 1- (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3,5-difluoro-4- (3-fluoro-4-trifluoromethoxyphenyl) benzene ((1) In the formula, n = 3, ring E = 1,4-cyclohexylene, G = covalent bond, L = 3,5-difluoro-
1,4-phenylene, ring Z = 3-fluoro-1,4-phenylene, k = 1, l = 0, m = 0, Q = -O-, Y =
Production of compound (No. 77) which is CF ₃

(First stage) 4- (3,5-difluorophenethyl) -synthesized in the same manner as in Example 1.
5.0 g of 1- (3-fluoropropyl) cyclohexane
THF (50 ml) was added to (17.6 mmol), and the mixture was cooled to -50 ° C under a nitrogen gas atmosphere. 13 ml of a hexane solution of 1.68 N normal butyl lithium (21.8
mmol) with a syringe and stirred at the same temperature for 1 hour, and then 0.5 (mol / l) zinc chloride THF solution 4
3.6 ml (21.8 mmol) was added dropwise. After the dropping was completed, the temperature of the reaction product was warmed to room temperature and further stirred for 2 hours. After adding 500 mg of tetrakistriphenylphosphine palladium as a catalyst to this reaction liquid, 3-fluoro-4-trifluoromethoxy bromobenzene 5.6 was added.
4 g (21.8 mmol) was added dropwise, and the mixture was refluxed for 2 hours.
The reaction solution was added to chilled 6N hydrochloric acid, the product was extracted with toluene, and the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water,
Dry over magnesium sulphate, then remove the solvent by evaporation 7.7.
g yellow suspension was obtained. Toluene / heptane = 1
/ 1 as a developing solvent, and purified by column chromatography on silica gel, and then recrystallized to give 1- (2
-(4- (3-Fluoropropyl) cyclohexyl) ethyl) -3,5-difluoro-4- (3-fluoro-4)
0.58 g (1.25 mmol) of trans-form of -trifluoromethoxyphenyl) benzene was obtained. Yield 7.1
%. C-I point 44.8 ° C, (N-I point 13.6 ° C). 1
H-NMR (CDCl3) δ (ppm): 7.38-
6.77 (m, 5H), 4.69 (t, 1H), 4.1
6 (t, 1H), 2.65 (t, 2H), 1.84-
0.93 (m, 16H).

Example 6 1- (2- (4- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) ethyl) -4-trifluoromethylbenzene (n = 3 in the formula (1), ring E =
G = 1,4-cyclohexylene, L = covalent bond, ring Z =
1,4-phenylene, k = 1 = 0, m = 1, Q = covalent bond, Y = CF ₃ (Compound (No. 18))

(First stage) 128 g (370 mmol) of methoxymethyltriphenylphosphine chloride in THF
1 l was added, and potassium-t-butoxide 4 was added thereto at 0 ° C.
After adding 1.5 g (370 mmol), 3 at that temperature
Stir for hours. 50.0 g (287 mmol) of commercially available 4-trifluoromethylbenzaldehyde was added to this reaction solution.
A 00 ml THF solution was added dropwise, and the mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. Water 1.5 in this reaction solution
l was added, the product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The yellow solution obtained by distilling off the solvent was converted into heptane /
It was purified by column chromatography on silica gel using ethyl acetate = 3/2 as a developing solvent, and the purified product was distilled under reduced pressure using a Vigreux tube. Thus 9 Tor
under r.b. 1-trifluoromethyl-4 at p93.5 ° C
19.5 g of (-2-methoxyvinyl) benzene (9
6.5 mmol) was obtained. Yield 33.6%.

(Second stage) The above 1-trifluoromethyl-
4- (2-methoxyvinyl) benzene 19.5 g (9
(6.5 mmol) was dissolved in 100 ml of acetone, 100 ml of 6N hydrochloric acid was added to this solution, and the mixture was stirred for 5 hours. The product was extracted with ethyl acetate, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent was distilled off, and 4-trifluoromethylbenzyl aldehyde was added to 1
7.5 g (93.0 mmol) was obtained. Yield 96.4%.

(Third step) 200 ml of ethanol was added to 17.5 g (93.0 mmol) of 4-trifluoromethylbenzyl aldehyde, and the mixture was cooled to 0 ° C. under a nitrogen gas atmosphere. Sodium borohydride (1.78 g, 47.1 mmol) was added thereto so that the liquid temperature did not exceed 10 ° C, and the mixture was stirred at 0 ° C for 2 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. After distilling off the solvent, 100 ml of HBr water (47%) was added to about 18 g of the residue and the mixture was refluxed for 7 hours.
Then, vacuum distillation was performed using a Vigreux tube. Thus 9
B. Under Torr. 19.5 g (77.1 m) of 2- (4-trifluoromethylphenyl) bromoethane at 94 ° C.
mol) was obtained. Yield 82.9%.

(Fourth stage) 19.5 g (77.1 m) of 2- (4-trifluoromethylphenyl) bromoethane as described above
mol) and dried magnesium 1.90 g (78.2)
of the Grignard reagent prepared in 100 ml ether solvent was cooled to 0 ° C., and 19.4 g of bicyclohexanedione monopropylene ketal (7
6.9 mmol) in 100 ml ether solution,
The mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was added to 100 ml of 6N hydrochloric acid, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. 300 ml of toluene and 1.5 g of Amberlyst were added to about 30 g of the obtained pale yellow oily substance, and the mixture was refluxed for 4 hours while removing water produced by the reaction with Gene Stark. The amberlyst was filtered off, the solvent was distilled off, and the residue was purified by column chromatography on silica gel using ethyl acetate / toluene = 1/1 as a developing solvent.
(4-oxocyclohexyl) -1- (2- (4-trifluoromethylphenyl) ethyl) -1-cyclohexene propylene acetal 20.0 g (48.9 mmo)
1) was isolated. This was hydrogenated in an ethanol solution in the presence of 1.0 g of 5% Pd / C catalyst. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. Formic acid 2 in the balance
After adding 0.0 g (444 mmol) and 100 ml of toluene and refluxing for 5 hours, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was treated with ethyl acetate / toluene = 1/3 as a developing solvent,
The product was purified by column chromatography on silica gel, and the purified product was recrystallized from heptane to give 4- (4
-Oxocyclohexyl) -1- (2- (4-trifluoromethylphenyl) ethyl) cyclohexane was added to 2.7
g (7.7 mmol) was isolated. The yield of this product from bicyclohexanedione monopropylene ketal is 1
It was 0.0%.

(5th step) 1,3-dioxan-2-ylethyltriphenylphosphine bromide 6.80 g (1
THF (70 ml) was added to 4.9 mmol), and potassium-t-butoxide (1.68 g, 14.9 mm) was added thereto at 0 ° C.
ol) was added, and the mixture was stirred at that temperature for 3 hours. 4- (4-oxocyclohexyl) -1-
(2- (4-Trifluoromethylphenyl) ethyl) cyclohexane 2.7 g (7.7 mmol) of 10 ml T
The HF solution was added dropwise, and the mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. 50 ml of water was added to this reaction solution,
The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The residue obtained by distilling off the solvent was converted to heptane / ethyl acetate = 3.
Purification was carried out by column chromatography on silica gel using 1/1 as the developing solvent, and the solvent was distilled off. The residue, 3.2 g, was hydrogenated in an ethanol solution in the presence of 0.15 g of 5% Pd / C catalyst. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. The residue was recrystallized from heptane / ethanol = 5/1 to give 4- (4- (1,3-dioxan-2-ylethyl) cyclohexyl) -1- (2-
1.46 g (3.23 mmol) of (4-trifluoromethylphenyl) ethyl) cyclohexane was obtained. 4- (4-oxocyclohexyl) -1- (2-
The yield from (4-trifluoromethylphenyl) ethyl) cyclohexane was 42%.

(Sixth stage) 4- (4- (1,3-dioxan-2-ylethyl) cyclohexyl) -1-
(2- (4-Trifluoromethylphenyl) ethyl) cyclohexane 1.46 g (3.23 mmol) was added with formic acid 1.5 g (33 mmol) and toluene 10 ml to give 5
After refluxing for an hour, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent is distilled off and 3-
1.21 g (3.07 mmol) of (4- (4- (2- (4-trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) propanal was obtained. Yield 9
5.0%.

(Seventh stage) 3- (4- (4- (2-
(4-trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) propanal 1.21 g
10 ml of ethanol was added to (3.07 mmol), and the mixture was cooled to 0 ° C. under a nitrogen gas atmosphere. 0.13 g of sodium borohydride so that the liquid temperature does not exceed 10 ° C.
(3.43 mmol) was added and the mixture was stirred at 0 ° C. for 2 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The solvent was distilled off to obtain 1.20 g (3.03 mmol) of 3- (4- (4- (2- (4-trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) propanol. Yield 98.7%.

(Eighth stage) 3- (4- (4- (2-
(4-Trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) propanol 1.20 g
Dimethoxyethane (10 ml) was added to (3.03 mmol), diethylaminosulfur trifluoride (DAST) 1.13 g (7.01 mmol) was added dropwise thereto, and the mixture was refluxed for 5 hours. The product was extracted with toluene, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography on silica gel using heptane as a developing solvent, and the solvent was distilled off. The residue was recrystallized from ethanol / heptane = 9/1, and 1- (2- (4- (4- (3-
Fluoropropyl) cyclohexyl) cyclohexyl)
Only 0.60 g (1.5 mmol) of trans form of ethyl) -4-trifluoromethylbenzene was isolated. Yield 49.5%. S _B -I point 118.9 ° C. 1H-NMR
(CDCl3) δ (ppm): 7.52 (d, 2H),
7.27 (d, 2H), 4.68 (t, 1H), 4.1
6 (t, 1H), 2.68 (t, 2H), 1.75-
0.99 (m, 26H).

Example 7 1- (2- (4- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) ethyl) -4-trifluoromethoxybenzene (n = 3 in the formula (1), ring E)
= 1,4-cyclohexylene, G = covalent bond, L = 1,
4-cyclohexylene, ring Z = 1,4-phenylene, k
= 1 = 0, m = 1, Q = -O-, Y = CF ₃ (No. 19))

(First stage) 350 g (1.02 mol) of methoxymethyltriphenylphosphine chloride in THF
1.8 l was added, and 114 g (1.02 mol) of potassium t-butoxide was added thereto at 0 ° C., and then the mixture was stirred at that temperature for 3 hours. Commercially available 4-trifluoromethoxybenzaldehyde 150.0 g (0.79 mo)
A 750 ml THF solution of 1) was added dropwise, and the mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. After adding 1.5 l of water to the reaction solution and extracting the product with ethyl acetate,
The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The yellow solution obtained by distilling off the solvent was purified by column chromatography on silica gel using heptane / ethyl acetate = 3/2 as a developing solvent,
The purified product was distilled under reduced pressure using a Vigreux tube. Thus under 9 Torr b. 138 g of 1-trifluoromethoxy-4- (2-methoxyvinyl) benzene at 91 ° C
(0.63 mol) was obtained. Yield 79.7%.

(Second stage) 138 g (0.1%) of 1-trifluoromethoxy-4- (2-methoxyvinyl) benzene described above.
(63 mol) was dissolved in 500 ml of acetone, 500 ml of 6N hydrochloric acid was added to this solution, and the mixture was stirred for 5 hours. The product was extracted with ethyl acetate, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent was distilled off to give 4-trifluoromethoxybenzyl aldehyde 123
g (0.60 mol) was obtained. Yield 95.2%.

(Third step) To 123 g (0.60 mol) of 4-trifluoromethoxybenzyl aldehyde described above, 1.5 l of ethanol was added, and the mixture was cooled to 0 ° C. under a nitrogen gas atmosphere. 11.7 g (0.31 mol) of sodium borohydride was added to this so that the liquid temperature did not exceed 10 ° C., and the mixture was stirred at 0 ° C. for 2 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. After distilling off the solvent, HBr water (47
%) (750 ml) and refluxed for 7 hours, and then distilled under reduced pressure using a Vigreux tube. Thus under 1 Torr b. At 52.0 ° C., 52.8 g (0.20 mol) of 2- (4-trifluoromethoxyphenyl) bromoethane
Obtained. Yield 33.3%.

(Fourth stage) 25.0 g (92.9) of 2- (4-trifluoromethoxyphenyl) bromoethane as described above.
2.26 g (93.
(0 mmol) and 100 ml of a Grignard reagent prepared in an ether solvent were cooled to 0 ° C., and 22.0 g of bicyclohexanedione monopropylene ketal was added thereto.
A 100 ml ether solution of (87.2 mmol) was added dropwise, and the mixture was warmed to room temperature and stirred for 3 hours. This reaction solution is 6N
After adding to 100 ml of hydrochloric acid and extracting the product with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. To the residue were added 300 ml of toluene and 2.0 g of Amberlyst, and the mixture was refluxed for 5 hours while removing water produced by the reaction with Gene Stark. The amberlyst was filtered off, the solvent was distilled off, and the residue was purified by column chromatography on silica gel using ethyl acetate / toluene = 1/2 as a developing solvent to give 4- (4-oxocyclohexyl). ) -1- (2- (4-Trifluoromethoxyphenyl) ethyl) -1-cyclohexene propylene acetal 22.2 g (52.3 mmol) was isolated. This was hydrogenated in an ethanol solution in the presence of 1.2 g of 5% Pd / C catalyst. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. Formic acid 20.0 g (444 mmo)
l) and 100 ml of toluene were added and the mixture was refluxed for 5 hours. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography on silica gel using ethyl acetate / toluene = 1/3 as a developing solvent, and the purified product was recrystallized from heptane to give 4- (4-oxo). 5.7 g (15.6 mm) of cyclohexyl) -1- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexane.
ol) isolated. Bicyclohexanedione of this thing
The yield based on monopropylene ketal was 17.9%.

(5th stage) 1,3-dioxan-2-ylethyltriphenylphosphine bromide 10.0 g (2
THF (100 ml) was added to 1.9 mmol), and potassium-t-butoxide (2.46 g, 21.9 m) was added thereto at 0 ° C.
(mol) and then stirred at that temperature for 3 hours. 4- (4-oxocyclohexyl) -1 above was added to this reaction solution.
-(2- (4-trifluoromethoxyphenyl) ethyl) cyclohexane 5.7 g (15.6 mmol) of 2
A 0 ml THF solution was added dropwise, and the mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. 100m of water in this reaction liquid
l was added, the product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The residue obtained by distilling off the solvent was purified by column chromatography on silica gel using heptane / ethyl acetate = 3/1 as a developing solvent, and the solvent was distilled off. The residue, 5.1 g, was hydrogenated in an ethanol solution in the presence of 0.30 g of 5% Pd / C catalyst. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. Residue in heptane /
Recrystallized with ethanol = 5/1, 4- (4- (1,3-
Dioxan-2-ylethyl) cyclohexyl) -1-
(2- (4-trifluoromethoxyphenyl) ethyl)
3.25 g (6.94 mmol) of cyclohexane was obtained. 4- (4-oxocyclohexyl) -1
The yield from-(2- (4-trifluoromethoxyphenyl) ethyl) cyclohexane was 44.5%.

(Sixth stage) 4- (4- (1,3-dioxan-2-ylethyl) cyclohexyl) -1-
(2- (4-trifluoromethoxyphenyl) ethyl)
Formic acid 3.0 g (66 mmol) and toluene 20 ml were added to cyclohexane 3.25 g (6.94 mmol) 5
After refluxing for an hour, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent is distilled off and 3-
2.70 g (6.58 mmol) of (4- (4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) propanal was obtained. Yield 9
4.8%.

(Seventh stage) 3- (4- (4- (2-
(4-Trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) propanal 2.70 g
20 ml of ethanol was added to (6.58 mmol), and the mixture was cooled to 0 ° C. under a nitrogen gas atmosphere. 0.13 g of sodium borohydride so that the liquid temperature does not exceed 10 ° C.
(3.43 mmol) was added and the mixture was stirred at 0 ° C. for 2 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from heptane to give 3- (4-
2.10 g (5.09 mmol) of (4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) propanol was obtained. Yield 77.4
%.

(Eighth stage) 3- (4- (4- (2-
(4-Trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) propanol 2.10 g
20 ml of dimethoxyethane was added to (5.09 mmol), 1.73 g (10.7 mmol) of diethylaminosulfur trifluoride (DAST) was added dropwise thereto, and the mixture was refluxed for 5 hours. The product was extracted with toluene, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The solvent was distilled off, and the residue was heptane / toluene = 3.
Purification was carried out by column chromatography on silica gel using 1/1 as the developing solvent, and the solvent was distilled off. The residue was recrystallized from ethanol and 1- (2- (4- (4- (3-
Fluoropropyl) cyclohexyl) cyclohexyl)
0.88 g (2.12 mmol) of only the trans form of ethyl) -4-trifluoromethylbenzene was isolated. Yield 41.7%. S _B -N point 73.8 ° C, NI point 13
1.8 ° C. 1H-NMR (CDCl3) δ (ppm):
7.20 (d, 4H), 4.68 (t, 1H), 4.1
5 (t, 1H), 2.62 (t, 2H), 1.75-
0.99 (m, 26H).

Example 8 1- (4- (3-fluoropropyl) cyclohexyl)
-3-fluoro-4-trifluoromethoxybenzene (n = 3 in the formula (1), ring E = 1,4-cyclohexylene, G, L = covalent bond, ring Z = 3-fluoro-1,
4-phenylene, k = 1, l = m = 0, Q = -O-, Y
Of the compound (No. 13) in which ═CF ₃

(First stage) 500 g of 1,3-dioxan-2-ylethyltriphenylphosphine bromide (1.
THF (3 l) was added to (09 mol), potassium-t-butoxide (122 g, 1.09 mol) was added thereto at 0 ° C, and the mixture was stirred at that temperature for 3 hr. Cyclohexanedione monoethylene ketal 141.9 g was added to this reaction liquid.
700 ml of THF solution (0.91 mol) was added dropwise,
The mixture was stirred at that temperature for 1 hour and then brought to room temperature and stirred for 3 hours. After adding 2 liters of water to the reaction solution and extracting the product with ethyl acetate, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The residue obtained by distilling off the solvent was purified by column chromatography on silica gel using heptane / ethyl acetate = 1/1 as a developing solvent, and the solvent was distilled off. The residue was hydrogenated in an ethanol solution in the presence of 3.0 g of 5% Pd / C catalyst.
After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under reduced pressure, and 4
98 g of -oxo-1- (1,3-dioxan-2-ylethyl) cyclohexane monoethylene acetal
(0.38 mol) was obtained. The yield of this product from cyclohexanedione monoethylene ketal was 42%.

(Second stage) 4-oxo-1- (1,
3-dioxan-2-ylethyl) cyclohexane To 60 g (234 mmol) of ethylene acetal was added 200 ml of 3N hydrochloric acid and 200 ml of acetone, and the mixture was stirred for 5 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate.
The residue obtained by distilling off the solvent was purified by column chromatography on silica gel using heptane / ethyl acetate = 3/2 as a developing solvent, and the solvent was distilled off to give 4
35.5 g (167 mmol) of -oxo-1- (1,3-dioxan-2-ylethyl) cyclohexane was obtained. Yield 71.3%.

(Third stage) 60% sodium hydride 7.12 in 280 ml of dimethoxyethane under a nitrogen gas atmosphere.
g (178 mmol) was added, and the mixture was stirred at room temperature for 10 minutes. 40.0 g of ethyl diethylphosphonoacetate in this solution
(178 mmol) was added dropwise, and the mixture was stirred at that temperature until the generation of hydrogen gas was completed.
30.0 g (141 mmol) of 1- (1,3-dioxan-2-ylethyl) cyclohexane was added dropwise so that the liquid temperature did not exceed 30 ° C., and the mixture was stirred for 30 minutes. The reaction solution was added to 300 ml of water, the product was extracted with ether, and the organic layer was dried over magnesium sulfate. The solvent was distilled off, and the residue 36.6 g was hydrogenated in an ethanol solution in the presence of 1.8 g of 5% Pd / C catalyst. After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under reduced pressure, and ethyl 2- (4
30.2 g (106 mmol) of-(1,3-dioxan-2-ylethyl) cyclohexylethanoate was obtained. The yield of this product from 4-oxo-1- (1,3-dioxan-2-ylethyl) cyclohexane was 75.
It was 1%.

(Fourth stage) The above ethyl 2- (4-
450 ml of toluene was added to 30.2 g (106 mmol) of (1,3-dioxan-2-ylethyl) cyclohexylethanoate under a nitrogen gas atmosphere, and the mixture was cooled to -65 ° C. To this solution, 120 ml of diisobutylaluminum hydride toluene solution (1.01 mol / l) (1
(21 mmol) was added dropwise, and the mixture was stirred at that temperature for 45 minutes, then 33 ml of saturated aqueous ammonium chloride solution was added dropwise, and the mixture was warmed to room temperature. Add 100 ml of ether to the reaction mixture,
Stir at that temperature for 1.5 hours and add 10% magnesium sulfate.
After adding g and stirring for 1 hour, the reaction solution was filtered. The filtrate was washed with water, dried over magnesium sulfate, and the solvent was evaporated to give 2 (4- (1,3-dioxan-2-ylethyl) cyclohexyl) ethanal (22.0 g, 91.
5 mmol) was obtained. Yield 86.3%.

(Fifth stage) 9.3 g (38.7 mmo) of 3-fluoro-4-trifluoromethoxybromobenzene
l) and 0.97 g of dried magnesium (39.9 mm)
ol) and the Grignard reagent prepared in 50 ml ether solvent was cooled to 0 ° C., and the above 2- (4-
40 g of (1,3-dioxan-2-ylethyl) cyclohexyl) ethanal 6.3 g (26.2 mmol)
l ether solution was added dropwise, warmed to room temperature and stirred for 3 hours. The reaction solution was added to 100 ml of 6N hydrochloric acid, the product was extracted with ethyl acetate, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, and the solvent was evaporated. To the residue were added 150 ml of toluene and 3.0 g of Amberlyst, the mixture was refluxed for 5 hours while removing water produced by the reaction with Gene Stark, and then 1.0 g (13.1 mmol) of trimethylene glycol was added and further refluxed for 1 hour. . The amberlyst was filtered off, the solvent was distilled off, and the residue was purified by column chromatography on silica gel using ethyl acetate / toluene = 1/2 as a developing solvent. -(2-
5.5 g (13.7 mmol) of (4- (1,3-dioxan-2-ylethyl) cyclohexyl) vinyl-3-fluoro-4-trifluoromethoxybenzene were isolated. 2- (4- (1,3-dioxane-2-
The yield based on ylethyl) cyclohexyl) ethanal was 52.3%.

(Sixth stage) 1- (2- (4- (1,
Hydrogenation of 5.5 g (13.7 mmol) of 3-dioxan-2-ylethyl) cyclohexyl) vinyl-3-fluoro-4-trifluoromethoxybenzene in an ethanol solution in the presence of 0.3 g of 5% Pd / C catalyst. did.
After completion of the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. 2.8 g (60.8 mmol) of formic acid and 50 toluene in the residue
After adding ml and refluxing for 5 hours, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over magnesium sulfate. The solvent was distilled off to obtain 1.76 g (5.1 mmol) of 3- (4- (2- (3-fluoro-4-trifluoromethoxyphenyl) ethyl) cyclohexyl) propanal. 1- (2- (4- (1,3-dioxan-2-ylethyl) cyclohexyl) vinyl-3-fluoro-4-
Yield from trifluoromethoxybenzene is 37.2%
Met.

(Seventh stage) 3- (4- (2- (3-
Fluoro-4-trifluoromethoxyphenyl) ethyl) cyclohexyl) propanal 1.76 g (5.
1 ml) was added with 12 ml of ethanol and cooled to 0 ° C. under a nitrogen gas atmosphere. Sodium borohydride 0.19 g (5.0 mm) so that the liquid temperature does not exceed 10 ° C
ol) was added and the mixture was stirred at 0 ° C. for 2 hours. The product was extracted with ethyl acetate, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from heptane to give 3- (4- (2- (3-
Fluoro-4-trifluoromethoxyphenyl) ethyl) cyclohexyl) propanol 1.52 g (4.4
mmol) was obtained. Yield 86.3%.

(Eighth stage) 3- (4- (2- (3-
Fluoro-4-trifluoromethoxyphenyl) ethyl) cyclohexyl) propanol 1.52 g (4.4
Dimethoxyethane (15 ml) was added to (mmol), DAST (1.40 g, 8.7 mmol) was added dropwise thereto, and the mixture was refluxed for 5 hours. The product was extracted with toluene, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water and dried over magnesium sulfate.
The solvent was distilled off, and the residue was purified by column chromatography on silica gel using heptane as a developing solvent, and the solvent was distilled off. Recrystallize the residue with ethanol and
-(3-Fluoropropyl) cyclohexyl) -3-fluoro-4-trifluoromethoxybenzene 0.12 g
(0.34 mmol) isolated. Yield 7.7%. PER
KIN-ELMER 7 Series Thermal
The clearing point measured by the Analysis System was −5.89 ° C. 1H-NMR (CDCl3) δ
(Ppm): 7.26 to 6.89 (m, 3H), 4.6
8 (t, 1H), 4.15 (t, 1H), 2.61
(T, 2H), 1.82-0.91 (m, 16H).

Example 9 1- (2- (4- (3-fluoropropyl) cyclohexyl)
Syl) ethyl) -3,5-difluoro-4- (4-
(1,1,2,3,3,3-hexafluoropropyl
(Xy) phenyl) benzene (in the formula (1), n =
3, ring E = 1,4-cyclohexylene, G = covalent bond,
L = 3,5-difluoro-1,4-phenylene, ring Z =
1,4-phenylene, k = 1, l = 0, m = 0, Q =-
O-, Y = CF ₂CFHCF₃Compound (No. 7)
4) Manufacturing

(First stage) 4- (3,5-difluorophenethyl) -synthesized in the same manner as in Example 1.
5.0 g of 1- (3-fluoropropyl) cyclohexane
THF (50 ml) was added to (17.6 mmol), and the mixture was cooled to -50 ° C under a nitrogen gas atmosphere. 14 ml of a hexane solution of 1.63N normal butyl lithium (22.8
mmol) with a syringe, and the mixture is stirred at the same temperature for 1 hour, and then 0.5 mol of zinc chloride in THF solution 45.6 m
1 (22.8 mmol) was added dropwise. After the dropping was completed, the temperature of the reaction product was warmed to room temperature and further stirred for 2 hours. After adding 500 mg of tetrakistriphenylphosphine palladium as a catalyst to this reaction solution, 4- (1,1,
7.37 g (22.8 mmol) of 2,3,3,3-hexafluoropropyloxy) bromobenzene was added dropwise.
Refluxed for 2 hours. This reaction liquid was cooled, and 6m hydrochloric acid 50m
In addition to 1, the product was extracted with toluene, the extract was washed successively with saturated aqueous sodium hydrogen carbonate and water, and then dried over magnesium sulfate.
Then, the solvent is distilled off, and the residue is toluene / heptane = 1 /
Purified by column chromatography on silica gel using 1 as a developing solvent, and then recrystallized from ethanol to give 1- (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3,5-difluoro. -4-
1.25 g (2.3 of 4- (1,1,2,3,3,3-hexafluoropropyloxy) phenyl) benzene
7 mmol) was obtained. Yield 13.5%.

The 1 H-NMR results well supported the structure.

Based on the description in Examples 1 to 9 and the section of the detailed description of the invention, the following compound No. 1 to No. Two
86 can be manufactured. Each compound is a compound represented by the general formula (1), in which n, ring E, k, G, l, L, m, ring Z and group Q-Y, which are parameters, are used.
Was displayed by extracting. In addition, among the parameters, the symbols H, B, and
M and D are 1,4-cyclohexylene,
1,4-phenylene,

[0206]

[Chemical 87]

That is, one in the G and L columns indicates a covalent bond.

[0208]

[Table 1]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

Example 10 (Using Example 1) 4- (4-propylcyclohexyl) benzonitrile 24% 4- (4-pentylcyclohexyl) benzonitrile 36% 4- (4-heptylcyclohexyl) benzonitrile 25% 4- ( A liquid crystal composition (A1) containing 15% of 4-pentylphenyl) benzonitrile was prepared. The clearing point of this nematic liquid crystal is 72.4 ° C., the threshold voltage at a cell thickness of 9 μm is 1.78 V, Δε is 11.0, and Δn is 0.13.
The viscosities at 7 and 20 ° C were 27.0 mPaS.
85% of this liquid crystal composition was added with the compound 1-of Example 1 of the present invention.
15% of (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3,5-difluoro-4- (3,5-difluoro-4-trifluoromethylphenyl) benzene was mixed to obtain a liquid crystal composition (B1). ) Was prepared. The threshold voltage of this product at a cell thickness of 8.8 μm is 1.39 V,
Δε is 12.0, Δn is 0.131, and elastic constant K33 /
K11 was 2.13. The extrapolated values calculated from the mixing ratio were Δε of 17.7 and Δn of 0.097, respectively. Also, this composition was placed in a freezer at -20 ° C.
After standing for 0 days, no precipitation of crystals was observed.

Example 11 (Use Example 2) 30% 4- (4-propylcyclohexyl) benzonitrile 4- (4-pentylcyclohexyl) benzonitrile 40% Liquid crystal consisting of 30% 4- (4-heptylcyclohexyl) benzonitrile A composition (A2) was prepared. This nematic liquid crystal has a clearing point of 52.3 ° C., a cell thickness of 9 μm, a threshold voltage of 1.60 V, Δε of 10.7, and Δn of 0.11.
The viscosities at 9 and 20 ° C. were 21.7 mPaS.
85% of this liquid crystal composition was added with the compound 1-of Example 2 of the present invention.
15% of (2- (4- (4- (2-fluoroethyl) cyclohexyl) cyclohexyl) ethyl) -4-trifluoromethoxybenzene was mixed to prepare a liquid crystal composition (B2). This product has a clearing point of 56.1 ° C and a cell thickness of 8.8.
The threshold voltage in μm is 1.55 V, Δε is 10.2,
Δn is 0.112, viscosity at 20 ° C is 22.3 mP
was aS. The extrapolated values calculated from the mixture ratios are 77.6 ° C. for the clearing point, 7.4 for Δε, and 0.0 for Δn.
The viscosities at 72 and 20 ° C. were 25.7 mPaS. The composition was left in a freezer at -20 ° C for 60 days, but no crystal precipitation was observed.

Example 12 (Using Example 3) The compound 1- (1- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) -3 of Example 4 of the present invention was added to 85% of the above liquid crystal composition (A2). , 5-difluoro-
15% of 4- (3-fluoro-4-trifluoromethoxyphenyl) benzene was mixed to prepare a liquid crystal composition (B3). This product has a clearing point of 64.5 ° C and a cell thickness of 8.8μ.
The threshold voltage at m is 1.52 V, Δε is 11.1, Δ
n is 0.122 and viscosity at 20 ° C. is 27.8 mPas.
It was S. The extrapolated values calculated from the mixing ratio were 133.6 ° C. for the clearing point, 13.4 for Δε, 0.139 for Δn, and the viscosity at 20 ° C. was 62.4 mPaS. Also, this composition was placed in a freezer at -20 ° C.
After standing for 0 days, no precipitation of crystals was observed.

Example 13 (Use Example 4) The compound 1- (2- (4- (3-fluoropropyl) cyclohexyl) ethyl) -3 of Example 5 of the present invention was added to 85% of the above liquid crystal composition (A1). , 5-difluoro-4- (3
15% of -fluoro-4-trifluoromethoxyphenyl) benzene was mixed to prepare a liquid crystal composition (B4). This product has a clearing point of 63.3 ° C., a cell thickness of 8.8 μm, a threshold voltage of 1.47 V, Δε of 11.4, and Δn of 0.
The viscosities at 130 and 20 ° C were 34.1 mPaS. The extrapolated values calculated from the mixing ratios are 15.7 ° C. for the clearing point, 13.7 for Δε, and 0.090 for Δn, respectively.
The viscosity at 0 ° C. was 67.5 mPaS. Also,
The composition was left in a freezer at -20 ° C for 60 days, but no precipitation of crystals was observed.

Example 14 (Using Example 5) The compound 1- (2- (4- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) of Example 6 of the present invention was added to 85% of the above liquid crystal composition (A1). ) Ethyl) -4-
15% of trifluoromethylbenzene was mixed to prepare a liquid crystal composition (B5). The clearing point of this product is 74.9 ° C,
The threshold voltage at a cell thickness of 8.9 μm is 1.79 V, Δε
Was 10.6, Δn was 0.130, and the viscosity at 20 ° C. was 29.7 mPaS. The extrapolated values calculated from the mixing ratios are 93.0 ° C. for the clearing point and 8.3 for Δε, respectively.
Δn is 0.090, viscosity at 20 ° C is 46.7 mP
was aS. The composition was left in a freezer at -20 ° C for 60 days, but no crystal precipitation was observed.

Example 15 (Use Example 6) The compound 1- (2- (4- (4- (3-fluoropropyl) cyclohexyl) cyclohexyl) of Example 7 of the present invention was added to 85% of the above liquid crystal composition (A1). ) Ethyl) -4-
15% of trifluoromethoxybenzene was mixed to prepare a liquid crystal composition (B6). This product has a clearing point of 77.1.
The threshold voltage at 1.degree. C. and the cell thickness of 8.7 .mu.m is 1.78 V,
Δε was 10.2, Δn was 0.130, and the viscosity at 20 ° C. was 27.8 mPaS. The extrapolated values calculated from the mixing ratios are 107.7 ° C. for the clearing point, 5.7 for Δε, 0.090 for Δn, and a viscosity at 20 ° C. of 3 respectively.
It was 2.9 mPaS. Moreover, this composition is -20 degreeC.
After leaving it in the freezer for 60 days, no precipitation of crystals was observed.

Example 16 (Use Example 7) The compound 1- (3-fluoropropyl) cyclohexyl of Example 8 of the present invention was added to 85% of the above liquid crystal composition (A1).
Liquid crystal composition (B7) was prepared by mixing 15% of -3-fluoro-4-trifluoromethoxybenzene. The Δε of this product was 9.9. In addition, Δε calculated from the mixing ratio
Was 3.7. The composition was left in a freezer at -20 ° C for 60 days, but no crystal precipitation was observed.

Example 17 (Comparative Example 1) 50% of the above-mentioned liquid crystal composition (A2) was used, and
No. 6817 discloses compound 1- (4) of the formula (5) reference
-(2-Fluoroethyl) cyclohexyl) -4-
(3,4,5-Trifluorophenyl) benzene 50%
Were mixed to prepare a liquid crystal composition (B4). On the other hand, 50% of the liquid crystal composition (A2) was mixed with the compound 1- (4-) of Example 2.
50% of (2-fluoroethyl) cyclohexyl) cyclohexyl) -4- (2- (4-trifluoromethoxyphenyl) ethyl) cyclohexane was mixed to prepare a liquid crystal composition (B5). These liquid crystal compositions B4 and B5
Each of them was left in a freezer at -20 ° C for 60 days. In the case of B5, no crystal precipitation was observed, but
In the case of B4, precipitation of crystals was observed.

Example 18 (Comparative Example 2) 1- (4- (4-ethylcyclohexyl) cyclohexyl) -3,4-difluorobenzene 16.67% 1- (4- (4-propylcyclohexyl) cyclohexyl) -3 , 4-difluorobenzene 16.67% 1- (4- (4-pentylcyclohexyl) cyclohexyl) -3,4-difluorobenzene 16.66% 1- (4- (2- (4-ethylcyclohexyl) ethyl) cyclohexyl ) -3,4-Difluorobenzene 10.00% 1- (4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl) -3,4-difluorobenzene 5.00% 1- (4- (2- ( 4-pentylcyclohexyl) ethyl) cyclohexyl) -3,4-difluorobenzene 10.00% 1- (4 -(4-Ethylcyclohexyl) phenyl) -3,4-difluorobenzene 6.25% 1- (4- (4-propylcyclohexyl) phenyl) -3,4-difluorobenzene 6.25% 1- (4- ( A liquid crystal composition (A3) consisting of 4-pentylcyclohexyl) phenyl) -3,4-difluorobenzene 12.50% was prepared. The compound (1- (2- (4- (4-propylcyclohexyl) cyclohexyl) ethyl) -4-) was added to 57% of the liquid crystal composition (A3).
Trifluoromethoxybenzene) 43% was mixed to prepare a liquid crystal composition (B9). On the other hand, the liquid crystal composition (A2) 5
0% to the compound of Example 7 (1- (2- (4- (4-
(3-Fluoropropyl) cyclohexyl) cyclohexyl) ethyl) -4-trifluoromethoxybenzene)
Was mixed at 43% to prepare a liquid crystal composition (B10). When each of these liquid crystal compositions B9 and B10 was left in a freezer at -40 ° C for 18 hours, no crystal precipitation was observed in the case of B10, but crystal precipitation was observed in the case of B9.

[0229]

INDUSTRIAL APPLICABILITY The compound of the present invention has a very large Δε, which sometimes exceeds 20, and in addition to the conventional high Δ
It overcomes poor compatibility and narrow liquid crystal range, which were problems common to compounds having ε, and has low viscosity and is chemically stable. A liquid crystal composition containing these compounds as components is extremely stable chemically, has a very large Δε, further reflects the good compatibility and wide liquid crystal range of the compound, and has a wide and practical temperature range. It has the excellent properties of exhibiting a nematic phase and low viscosity. Therefore, the composition obtained by using these compounds is very useful in forming a liquid crystal display device.

For example, in No. 17 and No. The compound of 19 has a resistivity and compatibility comparable to those of the compound (1), but has a large Δε and a large clearing point, and on the other hand, the viscosity is significantly decreased. And again
When compared with the compound (5), the clearing point, the viscosity, Δε and Δn are about the same, but the compatibility is significantly excellent,
It is useful as a composition component of a display device for TFT. In addition, No. 18, No. 70 and No. 70. 80 compounds are
It has a large Δε, good compatibility, a large Δn, and a high specific resistance value, and is therefore useful as a composition component of a display element for TFT. In addition, No. 240 compounds have Δε
Is large and Δn is large, and further, it has a property of significantly increasing the clearing point, and thus is very useful as a composition component.

No. The compound of 74 has a large Δε and a very large Δn, and is also excellent in compatibility,
It is also useful as a composition component of a display element for TFT. Two
No. of the ring compound. No. 13 has a low clearing point, but has a large Δε and an extremely low viscosity, and is therefore useful as a composition component of a display element for TFT.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/225 7419-4H C07C 43/225 C C09K 19/14 9279-4H C09K 19/14 19 / 30 9279-4H 19/30 19/42 9279-4H 19/42 G02F 1/13 500 G02F 1/13 500 (72) Inventor Yasuyuki Goto 462-2 Nishihiro, Ichihara-shi, Chiba (72) Inventor Etsushi Nakagawa Chiba 8890 Goi, Ichihara-shi, Japan (72) Inventor Shinichi Sawada 316-1, Nishihiro, Ichihara-shi, Chiba

Claims (17)

[Claims] 1. A general formula (I) ## STR1 ## _{F- (CH 2) n -E- (} CH 2 CH 2) k -G- (CH 2 CH 2) 1 -L- (CH 2 CH 2) _m- Z-Q-Y (I) (In the formula, n is an integer of 1 to 10, k, l and m are each independently an integer of 0 to 2, and ring E is 1 on the 6-membered ring. 1, more than one hydrogen atom may be replaced by a fluorine atom 1,
4-cyclohexylene group or 1,4-phenylene group, G and L are each independently a covalent bond or one or more hydrogen atoms on the 6-membered ring may be substituted with a fluorine atom, 1, 4-cyclohexylene group or 1,4
-A phenylene group is shown, but when it is a covalent bond, G is preferred, ring Z is a 1,4-phenylene group which may be fluorine-substituted, and Q is a covalent bond or -O-.
Y is a fluoroalkyl group having 1 to 3 carbon atoms or a fluorine atom. However, when ring E is a 1,4-cyclohexylene group and at least one of G and L is a covalent bond, k + l + m ≠ 0, and when Q is —O—, Y is a fluorine atom. There is no such thing. )). 2. The liquid crystallinity according to claim 1, wherein k, l and m are each independently 0 or 1, and ring E is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. Compound. 3. The liquid crystal compound according to claim 1, wherein k, l and m are each independently 0 or 1, and ring E is a 1,4-cyclohexylene group. 4. k is 1, l and m are 0, G is a covalent bond, and L is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. Item 4. The liquid crystal compound according to item 3. 5. The liquid crystal compound according to claim 4, wherein L is a 1,4-cyclohexylene group. 6. The liquid crystal compound according to claim 4, wherein L is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. 7. The k and l are 0, m is 1, G is a covalent bond, and L is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. The liquid crystal compound according to item 1. 8. The liquid crystal compound according to claim 7, wherein L is a 1,4-cyclohexylene group. 9. The liquid crystalline compound according to claim 7, wherein L is a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. 10. The k and m are 1, l is 0, G is a covalent bond, and L is a 1,4-cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. The liquid crystal compound according to item 1. 11. k is 1, l and m are 0, G and L
The liquid crystal compound according to claim 3, wherein is a covalent bond. 12. G and L are independently 1,4-
The liquid crystalline compound according to claim 1, which is a cyclohexylene group, a 1,4-phenylene group or a fluorine-substituted 1,4-phenylene group. 13. A liquid crystal composition comprising at least one kind of the liquid crystal compound according to claim 1. 14. The method according to claim 1 as the first component.
Contains at least one kind of liquid crystalline compound
As the second component, the general formulas (II), (III) and (I
V) [Chemical 2](In the formula, R₁Represents an alkyl group having 1 to 10 carbon atoms, V
Is F, Cl, CF₃, OCF₃, OCF₂H or carbon
Represents an alkyl group of the number 1 to 10, L₁, L₂, L ₃, L
_FourEach independently represent H or F, and Z₁, Z₂Is
Independently- (CH₂)₂-, -CH = CH-
Indicates a covalent bond, and ring A is trans-14-cyclohexyl.
Represents a silene group or a 1,4-phenylene group, and a is 1 or
Or 2 is shown, and b is 0 or 1. ) Consists of
Containing at least one compound selected from
A characteristic liquid crystal composition. 15. The method according to claim 1 as the first component.
Contains at least one kind of liquid crystalline compound
As the second component, general formulas (V), (VI), (VII),
(VIII) and (IX)(In the formula, R₂Is F, an alkyl group having 1 to 10 carbon atoms, or
An alkenyl group having 2 to 10 carbon atoms is shown. In which
And any methylene group (-CH₂−) Is the oxygen source
May be substituted by a child (-O-), but two or more
The above methylene groups are continuously replaced by oxygen atoms
Absent. Z₃Is-(CH₂)₂-, -COO or covalent bond
Indicates L_FiveAnd L₆Are independently H or F
Indicates D ₁Is trans-1,4-cyclohexylene
Group, 1,4-phenylene group or 1,3-dioxane-
2,5-diyl group is shown, and ring U is trans-1,4-diyl.
Represents a chlorhexylene group or a 1,4-phenylene group,
c and d each independently represent 0 or 1. ) [Chemical 4](In the formula, R₃Represents an alkyl group having 1 to 10 carbon atoms, L
₇Represents H or F, and e represents 0 or 1. ) [Chemical 5](In the formula, R_FourRepresents an alkyl group having 1 to 10 carbon atoms, and I
Is a trans-1,4-cyclohexylene group or 1,4
Represents a phenylene group, L₈, L₉Are independent of each other
Indicates H or F, and Z_FourIs -COO- or a covalent bond
, Z_FiveRepresents -COO- or -C≡C-,
f and g each independently represent 0 or 1. ) [Chemical 6](In the formula, R_Five, R₆Each independently has 1 to 10 carbon atoms.
Alkyl group, alkoxy group or alkoxymethyl group of
And W is a trans-1,4-cyclohexylene group,
1,4-phenylene group or 1,3-pyrimidine-2,
5-diyl group, K is trans-1,4-cyclohexyl
A xylene group or a 1,4-phenylene group, Z₆Is
-C≡C-, -COO-,-(CH₂)₂-Or shared
The result is shown below.(In the formula, R₇Is an alkyl group having 1 to 10 carbon atoms or ar
R represents a Coxy group₈Is an alkyl group having 1 to 10 carbon atoms
Show. R₈Any methylene group (-CH₂−) Is the oxygen source
May be substituted by a child (-O-), but two or more
The above methylene groups are continuously replaced by oxygen atoms
Absent. M is a trans-1,4-cyclohexylene group or
Represents a 1,3-pyrimidine-2,5-diyl group, a ring N
And P are each independently trans-1,4-cyclo
A hexylene group or a 1,4-phenylene group, Z₇
Is -COO-,-(CH₂)₂-, -CH = CH- or
Indicates co-bond, Z₈Is -C≡C-, -COO-, or
Represents a covalent bond, h represents 0 or 1, and L_TenIs H again
Indicates F. ) A compound selected from the group consisting of
A liquid crystal composition comprising at least one kind. 16. A liquid crystal compound according to any one of claims 1 to 12 is contained as a first component, and as a part of the second component, one of the general formulas (II), (III) and (IV ) Containing at least one compound selected from the group consisting of, and as the other part of the second component, a group consisting of general formulas (V), (VI), (VII), (VIII) and (IX) A liquid crystal composition comprising at least one selected compound. 17. A liquid crystal display device constituted by using the liquid crystal composition according to any one of claims 13 to 16.