JP2000169413A - Novel liquid crystal compound which is 6-trifluoromethoxynaphthalene derivative, liquid crystal composition containing the same and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel liquid crystal compound which is a 6-trifluoromethoxynaphthalene derivative which is excellent in liquid crystallinity, has low viscosity and good responsiveness, and can be used for an active matrix driving method. Provided are a liquid crystal composition containing the same and a liquid crystal element having the same as a constituent element. [Constitution] General formula (I) (R: C 1-20 alkyl group, alkoxyl group, etc.
Ring A, ring B: independently trans-1,4-cyclohexylene group, 1,4-phenylene group which can be substituted by F atom, L and M: CH ₂ CH ₂ , single bond, etc., X ^{1 to} X ³ : independently a liquid crystal compound represented by H atom or F atom)
A liquid crystal composition containing the same, a liquid crystal device having the same as a constituent element, and a method for producing the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel liquid crystal compound which is a 6-trifluoromethoxynaphthalene derivative useful as an electro-optical liquid crystal display material, a liquid crystal composition containing the same, and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art Liquid crystal display elements have been used in various measuring instruments such as watches and calculators, panels for automobiles, word processors, electronic organizers, printers, computers, televisions and the like. Typical liquid crystal display systems are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest / host) type or FLC capable of high-speed response. (Ferroelectric liquid crystal). As a driving method, a multiplex driving has been generally used instead of the conventional static driving, and a simple matrix method, more recently, an active matrix method has been put to practical use.

[0003] As the liquid crystal material used for these, a great variety of compounds have been synthesized so far, and they are used in accordance with the display system, drive system, or application thereof.

A liquid crystal compound is generally composed of a central skeleton portion called a core and side chain portions on both sides. Usually, at least one of the side chain portions is often a chain group, but in the case of a so-called p-type liquid crystal having a positive dielectric anisotropy, the other side chain portion is a polar group.

The polar groups used in liquid crystal compounds include:
A cyano group is typical. The liquid crystal compound having a cyano group has high polarity and excellent liquid crystallinity, but has a relatively large viscosity and cannot be used in the above-described active matrix driving method because a high voltage holding ratio cannot be obtained. There are many. Therefore, a fluorine atom is often used as a polar group. Since the liquid crystal compound having a fluorine atom as the polar group has a weaker polarity and a smaller dielectric anisotropy as compared with the above-described cyano-based liquid crystal compound, it is easy to obtain a low viscosity and a high voltage holding ratio, Particularly, it is suitable for an active matrix drive system.

Incidentally, these fluorine atoms used as polar groups are usually introduced in a structure directly connected to a phenyl group at a molecular terminal. Therefore, compounds are almost limited to compounds having a 4-fluorophenyl group, a 3,4-difluorophenyl group, or a 3,4,5-difluorophenyl group at one end of the molecule. Very small width. Therefore, these fluorine-based liquid crystal compounds alone cannot sufficiently meet the required characteristics of a liquid crystal composition which is becoming more advanced year by year.

A trifluoromethoxy group is known as a polar group whose properties are relatively similar to a fluorine atom.
The liquid crystal compound having a trifluoromethoxy group has a viscosity slightly smaller than the corresponding fluorine atom, and its polarity is weakened by the strong electron-withdrawing property of the trifluoromethyl group despite the presence of ether oxygen. Therefore, a high voltage holding ratio can be obtained, and the device can also be used in an active matrix driving system.

On the other hand, the ring structure constituting the core portion of the liquid crystal compound includes a 1,4-phenylene group (which may be substituted by one or two halogen atoms, a cyano group, a methyl group, etc.) and a trans- The 1,4-cyclohexylene group accounts for the majority. In addition, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group,
Heterocyclic systems such as 1,3-dioxane-trans-2,5-diyl group, transdecalin-2,6-diyl group, naphthalene-2,6-diyl group, tetralin-2,6-diyl group, bicyclo Condensed ring systems such as [2,2,2] octane-1,4-diyl group and spiro [3,3] heptane-2,6-diyl group are also being studied.

By the way, in the case of ordinary p-type liquid crystal, the polar group needs to be directly connected to an aromatic ring in order for the above-mentioned polar group to exhibit its effect sufficiently. However, considering the application to the active matrix driving method, a heterocyclic compound cannot be used because a high retention cannot be obtained, and an aromatic ring which is considered to be usable is naphthalene-2,
The fact is that it is extremely limited, such as a 6-diyl group.

Liquid crystal compounds having a 6-cyanonaphthyl group have already been reported (D. Coates et al., Mol. Cryst. Liq. Cryst., 3
7 249 (1976)), and the 6-cyanonaphthyl group is 4
A cyanophenyl group and 4′-cyanobiphenyl-4-
It has been shown to have intermediate properties with yl groups.
In addition, according to studies by the present inventors, it has been found that the liquid crystal compound having the 6-cyanonaphthyl group has excellent response characteristics.

Therefore, a liquid crystal compound having a 6-cyanonaphthyl group to which a trifluoromethoxy group is directly bonded as a polar group can be used in an active matrix driving system, and has a low viscosity and good responsiveness. It is considered possible.

However, a liquid crystal compound such as a 6-trifluoromethoxynaphthalene derivative has not been known at all, partly because its synthesis was not easy, and its development is desired.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to provide a liquid crystal display device having excellent liquid crystal properties, low viscosity and good responsiveness in order to meet the above-mentioned object, and to be applicable to an active matrix drive system. Provided is a novel liquid crystal compound which is a possible 6-trifluoromethoxynaphthalene derivative, a liquid crystal composition containing the compound, and a liquid crystal element having the same as a constituent element.

[0014]

Means for Solving the Problems The present invention provides as means for solving the above problems: General formula (I)

Embedded image (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkoxylalkyl group, an alkenyl group or an alkenyloxy group.
May be substituted with one or two or more fluorine atoms, and ring A is trans-1,
4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, and 2,6-difluoro-1,4 which may be substituted by one or more fluorine atoms -Phenylene group, pyridine-2,5-
Diyl group, pyrimidine-2,5-diyl group, pyrazine-
Represents a 2,5-diyl group, a pyridazine-3,6-diyl group, a trans-1,3-dioxane-2,5-diyl group or a decahydronaphthalene-3,8-diyl group, and ring B is trans-1 1,4-cyclohexylene group, which may be substituted by one or more fluorine atoms,
4-phenylene group, 2-fluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2 , 5-diyl group, pyridazine-3,6
-Diyl group, trans-1,3-dioxane-2,5-
Represents a diyl group, a decahydronaphthalene-3,8-diyl group or a single bond, and L and M are each independently —CH _{2
CH 2 -, - CH 2 O} -, - OCH 2 -, - COO -, -
_{OCO -, - CF 2 O -} , - OCF 2 -, - CH 2 CH 2 C
H ₂ CH ₂ —, —CF ＝ CF—, —C≡C— or a single bond. When ring B represents a single bond, M represents a single bond.
X ^{1 to} X ³ each independently represent a hydrogen atom or a fluorine atom. )). 2. ^2. The liquid crystal compound according to the above item 1, wherein X ² represents a fluorine atom in the general formula (I). 3. In the general formula (I), L and M are each independently-
_3. The liquid crystal compound according to the above 1 or 2, which represents CH ₂ CH ₂ —, —COO—, —C≡C— or a single bond. 4. 4. The liquid crystalline compound according to the above 1, 2 or 3, wherein in formula (I), at least one of L and M represents a single bond. 5. The liquid crystalline compound according to the above 1, 2, 3 or 4, wherein in the general formula (I), R represents a linear alkyl group having 1 to 7 carbon atoms. 6. General formula (IIa)

Embedded image (Wherein, X ^{1 to} X ³ each independently represent a hydrogen atom or a fluorine atom, and Wa represents ^a chlorine atom, a bromine atom or an iodine atom). A process for producing a compound represented by the general formula (I) according to the above 1, wherein the compound is used as 7. 2. A liquid crystal composition containing the liquid crystal compound represented by the general formula (I) as described in 1 above. 8. A liquid crystal device comprising the liquid crystal composition according to the above item 7 as a constituent element. Has been found as a means for solving the problem.

DESCRIPTION OF THE PREFERRED EMBODIMENTS An example of the present invention will be described below. The present invention relates to a compound of the formula (I)

[0015]

Embedded image A novel liquid crystal compound which is a 6-trifluoromethoxynaphthalene derivative represented by the following formula:

In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkoxylalkyl group, an alkenyl group or an alkenyloxy group, which is an alkoxyl group having 1 to 7 carbon atoms or one or two of them. Although it may be substituted by two or more fluorine atoms, an alkyl group or an alkenyl group is preferable, and a linear alkyl group having 1 to 7 carbon atoms is particularly preferable. Ring A is trans-
1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group which may be substituted by one or more fluorine atoms, 2,6
-Difluoro-1,4-phenylene group, pyridine-2,
5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group or decahydronaphthalene Represents a 3,8-diyl group, but a trans-1,4-cyclohexylene group, 1,4-
A phenylene group, a 2-fluoro-1,4-phenylene group or a 2,6-difluoro-1,4-phenylene group is preferred. Ring B is a trans-1,4-cyclohexylene group, 1
1,4-phenylene group which may be substituted by one or more fluorine atoms, 2-fluoro-1,4-
Phenylene group, 2,6-difluoro-1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,
5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, decahydronaphthalene-3,8-
It represents a diyl group or a single bond, but when low viscosity is required, ring B is preferably a single bond, and has a high refractive index anisotropy (Δ
When n) is required, a 1,4-phenylene group, a pyridine-2,5-diyl group or a pyrimidine-2,5-diyl group is preferable, and when a very large dielectric anisotropy (Δε) is required. Has at least one of 2-fluoro-
1,4-phenylene group or 2,6-difluoro-1,4
-A phenylene group is preferred. L and M are each independently-
_{CH 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - COO
-, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2
CH ₂ CH ₂ CH ₂ —, —CF ＝ CF—, —C≡C— or a single bond, but —CH ₂ CH ₂ —, —COO—, —C}
C- or a single bond is preferable, and at least one is preferably a single bond. When ring B represents a single bond, M represents a single bond. X ^{1 to} X ³ each independently represent a hydrogen atom or a fluorine atom, at least one of which represents a fluorine atom, and when high liquid crystallinity is required, X ¹ and X ³
Are preferably hydrogen atoms, and particularly large Δε
Is required, at least one of X ^{1 to} X ³ , particularly X ^2, is preferably a fluorine atom. The 1,4-position of the cyclohexylene group and the 3,8-position of bicyclo [4,4,0] decane are in a trans configuration.

As described above, the compound represented by the general formula (I) can include a very wide variety of compounds depending on the selection of R, ring A, ring B, L, M and X ^{1 to} X ^3. In Although,
Among these, the compounds represented by the following formulas (Iaa) to (Inf) are preferred.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

Embedded image In the above equations, R ^a represents a linear alkyl group having 1 to 7 carbon atoms, R ^b represents a linear alkenyl group having 2 to 7 carbon atoms, particularly preferably a vinyl group or a 3-butenyl group Represent. R ^c represents a linear alkenyl group having 4 to 7 carbon atoms, particularly preferably a 3-butenyl group.

Further, in the above formula, (Iad), (Iae),
(Ice), (Ifa), (Ifb), (Ifc), (Ifd),
(Ife), (Iff), (Ifg), (Ifh), (Ifi),
(Ifk), (Ifm), (Iga), (Igb), (Igc),
(Igd), (Ige), (Igh), (Igi), (Ii
a), (Iib), (Iic), (Iid), (Iie), (Ik)
a), (Ikb), (Ikc), (Ikd), (Ima), (Im
b), (Imc), (Ina), (Inb), (Inc), (Inn)
d), (Ine), (Inf), (Ing), (Ipa), (I
The compounds pb), (Ipc), (Ipd), (Ipe) and (Ipf) are particularly preferred.

The compound of the general formula (I) of the present invention can be produced as follows depending on its R, ring A, ring B, L and M.

(I) In the case of compounds represented by formulas (Iaa) to (Iac): formula (IIb)

[0037]

Embedded image (Wherein, X ¹ to X ³ represents the same meaning as in general formula (I), W ^a chlorine, represents a halogen atom bromine or iodine, preferably .Z ^a methoxy group represents a bromine atom Or a phenolic hydroxyl group, a hydrogen atom or a trifluoromethoxy group protected by a protecting group such as benzyloxy.) To obtain a Grignard reagent by reacting with magnesium, or butyllithium or the like. To give an organometallic reagent, which is represented by the general formula (III)
a)

[0038]

Embedded image (Wherein ^Ra has the same meaning as in formulas (Iaa) to (Iac)), and then reacting the obtained cyclohexanol derivative with an acid catalyst. And the general formula (IV
a)

[0039]

Embedded image (Wherein, X ^{1 to} X ³ and ^Ra are the general formulas (Iaa) to (Ia)
c) and Z ^a have the same meaning as in formula (IIb). To obtain a cyclohexenylnaphthalene derivative represented by the following formula: This is catalytically reduced, and if necessary, a cyclohexane ring is isomerized to obtain a compound represented by the general formula (Va):

[0040]

Embedded image (Wherein, X ^{1 to} X ³ and ^Ra are the general formulas (Iaa) to (Ia)
c) and Z ^a have the same meaning as in formula (IIb). To obtain a cyclohexylnaphthalene derivative represented by the following formula: When Za is a protecting group for a phenolic hydroxyl group such as ^a methoxy group, it is deprotected with hydrobromic acid to obtain a compound of the general formula (VIa)

[0041]

Embedded image (Wherein, X ^{1 to} X ³ and ^Ra are the general formulas (Iaa) to (Ia)
Represents the same meaning as in c). To obtain a naphthol derivative represented by the formula: This is reacted with carbon disulfide in the presence of a strong base and then with an alkylating agent to give a compound of the general formula (VIIa)

[0042]

Embedded image (Wherein, X ^{1 to} X ³ and ^Ra are the general formulas (Iaa) to (Ia)
represents the same meaning as in c), and R 'represents a lower alkyl group. ) Can be obtained. Here, the strong base is preferably an alkali metal hydride such as sodium hydride, an alkyl lithium such as butyl lithium, a lithium amide such as lithium diisopropylamide, an alcoholate such as potassium t-butoxide, and the alkylating agent is methyl iodide. Preferred are ethyl iodide, methyl bromide, ethyl bromide, dimethyl sulfate or methyl p-toluenesulfonate. By reacting the dithiocarbonate with fluoride ions in the presence of a halonium ion generator, the above-mentioned general formula (Iaa)
To (Iac). Examples of halonium ion generators include N-iodosuccinimide (NIS) and N-bromosuccinimide (NB
S), N-chlorosuccinimide (NCS) or 1,3-dibromo-5,5-dimethylhydantoin (D
BH) and the like, and as a fluoride ion source, (tetrabutylammonium dihydrogen trifluoride (TBA)
H ₂ F ₃ ), a hydrogen fluoride-pyridine complex (HF-Py), a hydrogen fluoride-melamine complex (HF-mel), or the like can be used. When it has an aromatic ring, the aromatic ring may be halogenated by a halonium ion. In that case, the obtained compound can be obtained by lithiation of the obtained halide with an alkyl lithium such as butyl lithium and then protonation.

Here, instead of the cyclohexanone of the formula (IIIa), a compound of the general formula (IIIb) or (IIIc)

[0044]

Embedded image (Wherein, R ^a is Formula (Iaa) ~ (. Represents the same meaning as in Iac)) by using a 4-substituted cyclohexanone derivative represented by the general formula (Ica) ~
(Icd) and the compounds of the general formulas (Ida) to (Idc) can be produced in the same manner.

(Ii) In the case of the compounds represented by the general formulas (Iba) to (Ibc), the compound represented by the general formula (VIIIa) is used in place of the (IIIa) 4-alkylcyclohexanone in (i).

[0046]

Embedded image (Wherein ^Ra has the same meaning as in general formulas (Iaa) to (Iac).) Using a cyclohexaneethanal derivative represented by the following formula,
Each compound of ba) to (Ibc) can be produced.

Here, instead of the cyclohexaneethanal of the formula (VIIIa), the compound represented by the general formula (IXb), (IXc) or (IXd)

[0048]

Embedded image (Wherein ^Ra has the same meaning as in formulas (Iaa) to (Iac)), the use of aldehydes represented by formulas (Iea) to (Iec) and formulas (Ija) to The compound of (Ijf) can be produced in a similar manner.

(Iii) Formulas (Iad) to (Iaf)
In the case of the compound represented by the general formula (IIa)

[0050]

Embedded image (Wherein, X ¹ to X ³ represents the same meaning as in general formula (I), W ^a chlorine, represents a halogen atom bromine or iodine, preferably a bromine atom.) Is represented by A fluoronaphthalene derivative is reacted with magnesium to give a Grignard reagent, or is lithiated with an alkyl lithium such as butyl lithium to give an organometallic reagent, and has the formula (IIId)

[0051]

Embedded image With cyclohexane-1,4-dionemonoethylene acetal, dehydration in the presence of an acid catalyst, reacetalization if necessary, catalytic reduction, and deacetalization to obtain the general formula (Xa)

[0052]

Embedded image (Wherein, X ^{1 to} X ³ represent the same meaning as in the general formula (I)). The formula (XIa)

[0053]

Embedded image Is reacted with a Wittig reactant represented by the formula (I) and then hydrolyzed with an acid to give a compound of the general formula (XIIa)

[0054]

Embedded image (Wherein X ^{1 to} X ³ represent the same meaning as in the general formula (I)) to obtain a cyclohexanecarbaldehyde derivative represented by the following formula: The formula (XIb)

[0055]

Embedded image By reacting a Wittig reagent represented by the following formula, a compound in which ^Rb is a vinyl group in the general formulas (Iac) and (Iad) can be produced. Also, (XII
a) is reacted with the Wittig reagent of (XIa) two more times, and then reacted with the Wittig reagent of (XIb), whereby R ^b is a 3-butenyl group in the general formulas (Iad) to (Iaf). Compounds can be prepared.

Here, the cyclohexane of (IIId)
In place of 1,4-dione monoethylene acetal, a compound of the formula (IIIe)

[0057]

Embedded image The compounds of the general formulas (Ice) to (Ich) can be produced in the same manner by using the above bicyclohexane-4,4′-dione monoethylene acetal.

(Iv) In the case of the compounds represented by the general formulas (Ifa) to (Ifd): The organometallic reactant (or the Grignard reactant or the organolithium reactant) prepared from (IIb) is a trialkyl ester of boric acid. And then hydrolyzed with an acid. Organic boric acid and the like can also be used.
a)

[0059]

Embedded image (Wherein, R ^a represents the same meaning as in the general formula (Iaa) ~ (Iac), Y is. Representing a leaving group such as a halogen atom or a trifluoromethanesulfonyloxy group bromine or iodine) is represented by that benzene derivative is reacted in the presence of a transition metal catalyst, then, it can be prepared by converting a trifluoromethoxy group similarly Z ^a. Or the general formula (XIIb)

[0060]

Embedded image (Wherein, R ^a represents the same meaning as in the general formula (Iaa) ~ (Iac), W a is as in formula (IIb) represent the same meaning.) The organic prepared in a similar manner from benzene derivative of The metal reactant is represented by the general formula (IIc)

[0061]

Embedded image (Wherein, X ¹ to X ³ and Z ^a have the general formula (Iaa) ~ (Ia
Y has the same meaning as in c) and (IIb), and Y has the same meaning as in general formula (XIIa). ) Can be produced in the same manner as in the reaction with the naphthalene derivative represented by the formula (1). Here, the transition metal catalyst is preferably a palladium (0) complex, a palladium (II) complex, a nickel (II) complex or the like.

Here, the benzene derivatives of the general formulas (XIIc), (XIId), (XIIe) and (XIIf) are substituted for the benzene derivatives of the general formula (XIIa).

[0063]

Embedded image (Wherein, R ^a has the same meaning as in the general formulas (Iaa) to (Iac), Y has the same meaning as in the general formula (XIIa), and R ^c is a linear group having 4 to 7 carbon atoms. The compounds of the general formulas (Ife) to (Ifj) can be obtained by performing the same reaction using alkenyl groups. When the double bond of the alkenyl group is halogenated by a halonium ion, each compound of the general formulas (Ifk) to (Ifr) is obtained by dehalogenating the halide and regenerating the double bond. Can be.

Further, instead of the benzene derivative of (XIIa), a phenylcyclohexane derivative of the general formula (XIIg), (XIIh) or (XIIi)

[0065]

Embedded image (Wherein R ^a has the same meaning as in general formulas (Iaa) to (Iac), and Y has the same meaning as in general formula (XIIa)).
Each compound of a) to (Igj) can be produced.

Further, instead of the benzene derivative of (XIIa), a phenethylcyclohexane derivative of the general formulas (XIIj) and (XIIk)

[0067]

Embedded image (Wherein Ra has the same meaning as in general formulas (Iaa) to (Iac), and Y has the same meaning as in general formula (XIIa)).
Each compound of a) to (Ihf) can be produced.

The biphenyl derivatives of the general formulas (XIIm), (XIIn), (XIIo) and (XIIp) are substituted for the benzene derivatives of the formula (Xa).

[0069]

Embedded image (Wherein, R ^a has the same meaning as in general formulas (Iaa) to (Iac), Y has the same meaning as in general formula (XIIa), and R ^c has the same meaning as in general formula (XIIf). Is represented by the general formula (Ii).
Each compound of a) to (Iif) can be produced.
When the double bond of the alkenyl group is halogenated by a halonium ion, the halide is dehalogenated to regenerate the double bond, whereby the compound represented by the general formula (Ii)
g) to (Iim) can be obtained.

(V) Compounds represented by the general formulas (Ika) to (Ikc): a naphthalene derivative represented by the general formula (IIa) and a compound represented by the general formula (XIIIa)

[0071]

Embedded image (Where Ra represents the same meaning as in general formulas (Iaa) to (Iac)), and reacted with a phenylacetylene derivative in the presence of a transition metal catalyst and a copper (I) salt,
Compounds represented by formulas (Ika) to (Ikc) can be obtained.

Here, instead of the phenylacetylene derivative of (XIIIa), general formulas (XIIIb) and (XIIIb)
IIIc), general formula (XIIId) and general formula (XII)
Phenylacetylene derivatives of Ie)

[0073]

Embedded image (Wherein R ^a has the same meaning as in general formulas (Iaa) to (Iac), and R ^c has the same meaning as in general formula (XIIf)). ) To (Ikk).

Further, instead of the phenylacetylene derivative of the formula (XIIIa), the cyclohexylphenylacetylene derivative of the formulas (XIIIf) and (XIIIg) is used.

[0075]

Embedded image (Wherein Ra has the same meaning as in formulas (Iaa) to (Iac)), compounds represented by formulas (Ima) to (Imf) can be obtained in the same manner.

(Vi) In the case of compounds represented by the general formulas (Ina) to (Inc) The fluoronaphthalene derivative represented by the general formula (IIa) is reacted with magnesium to obtain a Grignard reagent, or butyllithium or the like. Lithiation with an alkyl lithium to give an organometallic reactant, and an arylboronic acid derivative by reacting with trimethyl borate,
This is oxidized with hydrogen peroxide to give a compound of the general formula (II)
d)

[0077]

Embedded image (Wherein, X ^{1 to} X ³ have the same meanings as in formulas (Iaa) to (Iac)), and a naphthol derivative represented by formula (XIVa) is obtained in the presence of a condensing agent.

[0078]

Embedded image (Wherein, R ^a is Formula (Iaa) ~ (. Represents the same meaning as in Iac)) formula by reaction with a benzoic acid derivative represented by (Ina) compound represented by the ~ (Inc) Can be obtained. Or (XIIa)
Alternatively, the acid chloride derivative may be reacted.

Here, the benzoic acid derivative of the general formula (XIVb), (XIVc), (XIVd) or (XIVe) is substituted for the benzoic acid derivative of the formula (XIVa).

[0080]

Embedded image (Wherein, R ^a has the same meaning as in general formulas (Iaa) to (Iac), and R ^c has the same meaning as in general formula (XIIf).) Compounds represented by formulas (Ind) to (Inp) can be obtained.

Further, instead of the benzoic acid derivative of (XIVa), the cyclohexylbenzoic acid derivatives of general formulas (XIVf), (XIVg) and (XIVh)

[0082]

Embedded image (Wherein, R ^a is Formula (Iaa) ~ (. Represents the same meaning as in Iac)) a or a compound represented by the general formula in the same manner (Ioa) ~ (Ioi) by using the acid chloride Obtainable.

Further, instead of the benzoic acid derivative of the formula (XIVa), the cyclohexylbenzoic acid derivatives of the formulas (XIVi), (XIVj) and (XIVk)

[0084]

Embedded image (In the formula, Ra represents the same meaning as in formulas (Iaa) to (Iac).) Or by using the acid chloride thereof, formulas (Ipa) to (Ipf) and formulas (Iqa) to The compound represented by (Iqc) can be obtained.

Compounds represented by the general formula (I) other than those described above can be produced in the same manner or by applying the same.

Many of the compounds represented by the general formula (I) show relatively excellent liquid crystal properties. Further, when a fluorine atom is introduced into the naphthalene ring in the same direction as the trifluoromethoxy group, the polarities are large and the properties as a strong p-type liquid crystal are exhibited. Further, it is excellent in compatibility with other liquid crystal compounds or liquid crystal compositions including general-purpose liquid crystals, so that it can be suitably used as a material for liquid crystal display cells in a state of a mixture thereof. The compound (I) of the present invention can be used in any of the above-mentioned various display methods, but is particularly suitable for use in a TN display element driven by a simple matrix or an active matrix and an STN display element.

As described above, preferable representative examples of the nematic liquid crystal compound which can be used by mixing with the compound represented by the general formula (I) include, for example, a phenyl benzoate derivative, a phenyl cyclohexane carboxylate derivative,
Biphenyl-4-yl cyclohexanecarboxylate derivative, phenyl cyclohexanecarbonyloxybenzoate derivative, phenyl cyclohexylbenzoate derivative, cyclohexyl cyclohexylbenzoate derivative, biphenyl derivative, cyclohexylbenzene derivative, terphenyl derivative, bicyclohexane derivative, 4-cyclohexylbiphenyl derivative A 4-phenylbicyclohexane derivative, a tercyclohexane derivative, a 1,2-dicyclohexylethane derivative, a 1,2-diphenylethane derivative,
1,2-diphenylethyne derivative, (2-cyclohexylethyl) benzene derivative, 4-phenethylbicyclohexane derivative, 4- (2-cyclohexylethyl) biphenyl derivative, 1- (4-phenyl) cyclohexyl-
2-cyclohexylethane derivative, 1- (4-cyclohexylphenyl) -2-phenylethyne derivative, phenylpyrimidine derivative, (4-biphenyl-4-yl) pyrimidine derivative, phenylpyridine derivative, (4-biphenyl-4-yl) And pyridine derivatives. For active use, biphenyl derivatives,
Cyclohexylbenzene derivatives, terphenyl derivatives,
Bicyclohexane derivative, 4-cyclohexylbiphenyl derivative, 4-phenylbicyclohexane derivative, tercyclohexane derivative, 1,2-dicyclohexylethane derivative, 1,2-diphenylethane derivative, 1,2-
Diphenylethyne derivative, (2-cyclohexylethyl) benzene derivative, 4-phenethylbicyclohexane derivative, 4- (2-cyclohexylethyl) biphenyl derivative, 1- (4-phenyl) cyclohexyl-2-cyclohexylethane derivative, 1- (4 -Cyclohexylphenyl) -2-phenylethyne derivative, and the like.

The effects of using the compound (I) of the present invention as a component of a liquid crystal composition are shown below.

[0089]

Embedded image

20% by weight of compound (b) and a general-purpose n-type host liquid crystal (H)

[0091]

Embedded image When a nematic liquid crystal composition (M-1) consisting of 80% by weight was prepared, the maximum liquid crystal phase temperature (T _NI ) was 77.2.
° C. This (M-1) was left at 150 ° C. for 20 hours. After cooling, the T _NI was measured to be 77.1 ° C.
Showed little change from before heating. Irradiation with ultraviolet light (1200 W / m ² ) for 20 hours showed no change in T _NI . On the other hand, this (M-1)
Was left at −20 ° C. for 2 weeks, but no precipitation of crystals or phase separation was observed. In addition, it is cooled to -60 ° C and crystallized,
Its melting point ( _TCN ) was measured to be -1 ° C.

Next, (M-1) is converted to a T cell having a cell thickness of 8.0 μm.
A liquid crystal element was prepared by filling in an N cell, and its electro-optical properties were measured. The results were as follows. Nematic phase maximum temperature (T _NI ) 77.2 ° C. Dielectric anisotropy (Δε) 1.6 Threshold voltage (Vth) 2.6 V Response time (τ) 30.0 ms Refractive index anisotropy (Δn) 0. [091] On the other hand, the physical properties and electro-optical properties of the host liquid crystal (H) alone are as follows. Nematic phase upper limit temperature (T _NI ) 72.5 ° C. Dielectric anisotropy (Δε) −1.3 Refractive index anisotropy (Δn) 0.085 Here, the response time is a rise time (τr) and a fall time. (Τd) is a response time at the time of applying a voltage at which the voltages become equal. The host liquid crystal (H) does not respond because it is n-type,
In (M-1), the dielectric anisotropy (Δε) is increased to 1.6 by adding 20% of (I-1), and 30.0%
High-speed response of m seconds has become possible. Moreover, the maximum temperature of the nematic phase (T _NI ) is 77.2 ° C. and the host liquid crystal (H)
4 ° C. or more as compared with. Further, it can be seen that the refractive index anisotropy (Δn) has also increased.

On the other hand, the 1-fluoro-2-cyanonaphthalene derivative (A)

[0094]

Embedded image A nematic liquid crystal composition (MA) comprising 20% by weight and 80% by weight of the host liquid crystal (H) was prepared. A liquid crystal element was prepared in the same manner, and its electro-optical characteristics were measured. The results were as follows. Nematic phase maximum temperature (T _NI ) 78.9 ° C. Dielectric anisotropy (Δε) 3.2 Threshold voltage (Vth) 2.14 V Response time (τ) 40.0 ms Refractive index anisotropy (Δn) 0. 106 (MA) indicates that T _NI is slightly higher than (M-1) and Δε
Is very large and Vth is low. However, it can be seen that the response time has increased. When the voltage holding ratio of this device was measured, the host liquid crystal (H) after heating was measured.
A considerable decrease was confirmed as compared with.

As described above, the compound (I-1) is excellent in compatibility with other liquid crystal compounds, has a high maximum temperature of the nematic phase, and greatly increases the dielectric anisotropy by the addition of the compound. The active matrix has the characteristics that the response and the refractive index anisotropy can be increased, and because it does not have a strong polar group in the molecule, it is easy to obtain a large specific resistance and a high voltage holding ratio. It is apparent that the compound can be used as a component of a driving liquid crystal material, and is superior to a conventionally known compound (A) having a relatively similar structure.

Accordingly, the compound of the general formula (I) can be used as a liquid crystal composition having a wide nematic phase temperature range, a low threshold voltage, capable of driving at a low voltage, and a high speed response. Very useful in preparation.

[0097]

EXAMPLES Examples of the present invention are shown below to further explain the present invention. However, the present invention is not limited to these examples.

The phase transition temperature was measured by a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).
Was performed in combination. The structure of the compound was confirmed by a nuclear magnetic resonance spectrum (NMR), an infrared resonance spectrum (IR), a mass spectrum (MS), and the like. “%” In the composition represents “% by weight”.

Example 1 Synthesis of 1-fluoro-2-trifluoromethoxy-6- (trans-4-propyl) cyclohexylnaphthalene (I-1)

While cooling in an ice water bath, 1.5 g of sodium hydride was suspended in 5 mL of tetrahydrofuran (THF), and 1-fluoro-6- (trans-4-propyl) cyclohexylnaphthalen-2-ol was added thereto. 0
g (this compound was prepared by adding a Grignard reagent prepared from 6-bromo-2-methoxynaphthalene and magnesium to 4-
After reacting with propylcyclohexanone and dehydrating in the presence of an acid to obtain a naphthylcyclohexene derivative, the cyclohexane ring is trans-isomerized with a strong base (potassium t-butoxy) in DMF and then dehydrogenated with hydrobromic acid. It was obtained by methylation and further fluorination with N-fluoro-5-trifluoromethoxypyridinium-2-sulfonate. ) THF solution 40m
L was added dropwise. After stirring for 1 hour, 30 mL of a THF solution of 7.4 g of S-ethyl chlorodithiocarbonate was added dropwise. After stirring for 1 hour, the reaction was stopped by adding 20 mL of water, and 50 mL of ethyl acetate was added.
After washing twice with 0 mL, dehydrated and dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give S-ethyl-O-fluoro-1- (trans-4-propylcyclohexyl) naphthalene-dithiocarbonate-dithiocarbonate. 12.0 g of 2-yl was obtained. This S-ethyl dithiocarbonate (12.0 g) was dissolved in dichloromethane (48 mL), and cooled to 0 ° C.
300 g of melamine complex and 1,3-dibromo-5,5
-To a 1 L dichloromethane solution of dimethylhydantoin was added dropwise. After stirring for 30 minutes, 200 mL of water was added to stop the reaction, and the organic layer was further washed twice with 200 mL of water.
It was dehydrated and dried with anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: hexane). Dissolve the whole amount in 50 mL of THF,
43 m 1.6 M butyllithium hexane solution at -78 ° C
L was added dropwise. Stir for 10 minutes after dropping, and add 10 mL of water
Was added. After returning to room temperature, 20 mL of water was further added. The organic layer was further washed twice with 20 mL of water, and then dried over anhydrous sodium sulfate. Purification by silica gel column chromatography (hexane / ethyl acetate = 9/1), recrystallization from ethanol, and 5-fluoro-6-trifluoromethoxy-2- (trans-4-propyl)
7.1 g of cyclohexylnaphthalene (I-1) was obtained.

Example 2 1,3-Difluoro-2-
Synthesis of trifluoromethoxy-6- (trans-4-propyl) cyclohexylnaphthalene

In Example 1, 1-fluoro-6-
In place of (trans-4-propyl) cyclohexylnaphthalen-2-ol, 1,3-difluoro-6- (trans-4-propyl) cyclohexylnaphthalene-2
-Ol (This compound is obtained by reacting a Grignard reagent prepared from 1,3-difluoro-6-bromo-2-methoxynaphthalene with 4-propylcyclohexanone and subjecting the naphthylcyclohexene derivative obtained by dehydration in the presence of an acid to catalytic reduction. After that, the cyclohexane ring is isomerized to trans with a strong base (potassium t-butoxy) in DMF and then demethylated with hydrobromic acid).
Similarly, the compound was converted into -S-ethyl-O-1,3-difluoro-6- (trans-4-propylcyclohexyl) naphthalen-2-yl dithiocarbonate, followed by trifluoromethoxylation to give 1,3-difluoro. -2-Trifluoromethoxy-6- (trans-4-propyl) cyclohexylnaphthalene was obtained.

The following compounds are obtained in the same manner as in Example 1 or 2.

2-trifluoromethoxy-6- (trans-4-propyl) cyclohexylnaphthalene 2-trifluoromethoxy-6- (trans-4-butyl) cyclohexylnaphthalene 2-trifluoromethoxy-6- (trans-4- Pentyl) cyclohexylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (trans-4-butyl) cyclohexylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (trans-4-pentyl) cyclohexylnaphthalene 1,3- Difluoro-2-trifluoromethoxy-6-
(Trans-4-butyl) cyclohexylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(Trans-4-pentyl) cyclohexylnaphthalene

Trans-4'-ethyl-trans-4-
(2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4'-propyl-trans-4- (2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4'-pentyl-trans-4- (2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4′-ethyl-trans-4- (1-fluoro-2-trifluoromethoxynaphthalen-2-yl)
Bicyclohexane trans-4'-propyl-trans-4- (1-fluoro-2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4'-pentyl-trans-4- (1-fluoro-2-tri Fluoromethoxynaphthalen-2-yl) bicyclohexane

Trans-4'-ethyl-trans-4-
(1,3-difluoro-2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4′-propyl-trans-4- (1,3-
Difluoro-2-trifluoromethoxynaphthalene-2
-Yl) bicyclohexane trans-4'-pentyl-trans-4- (1,3-
Difluoro-2-trifluoromethoxynaphthalene-2
-Yl) bicyclohexane trans-4'-ethyl-trans-4- (1,3,8
-Trifluoro-2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4'-propyl-trans-4- (1,3,
8-trifluoro-2-trifluoromethoxynaphthalen-2-yl) bicyclohexane trans-4′-pentyl-trans-4- (1,3
8-trifluoro-2-trifluoromethoxynaphthalen-2-yl) bicyclohexane

2-trifluoromethoxy-2- [4-
[2- (trans-4-propyl) cyclohexyl] ethyl] cyclohexylnaphthalene 2-trifluoromethoxy-2- [4- [2- (trans-4-pentyl) cyclohexyl] ethyl] cyclohexylnaphthalene 1-fluoro-2-tri Fluoromethoxy-2- [4-
[2- (trans-4-propyl) cyclohexyl] ethyl] cyclohexylnaphthalene 1-fluoro-2-trifluoromethoxy-2- [4-
[2- (trans-4-pentyl) cyclohexyl] ethyl] cyclohexylnaphthalene 1,3-difluoro-2-trifluoromethoxy-2-
[4- [2- (trans-4-propyl) cyclohexyl] ethyl] cyclohexylnaphthalene 1,3-difluoro-2-trifluoromethoxy-2-
[4- [2- (trans-4-pentyl) cyclohexyl] ethyl] cyclohexylnaphthalene

Example 3 Synthesis of 1-fluoro-2-trifluoromethoxy-6- [2- (trans-4-propylcyclohexyl) ethyl] naphthalene

In Example 2, 1,3-difluoro-
In place of 6-bromo-2-methoxynaphthalene, 1-fluoro-6-bromo-2-methoxynaphthalene was used,
4-Propylcyclohexaneethanal was used in place of 4-propylcyclohexanone, and 1-fluoro-2-trifluoromethoxy-6- [2- (trans −
4-propylcyclohexyl) ethyl] naphthalene was obtained.

In the same manner, the following compound is obtained.

2-trifluoromethoxy-6- [2-
(Trans-4-propylcyclohexyl) ethyl] naphthalene 2-trifluoromethoxy-6- [2- (trans-4
-Pentylcyclohexyl) ethyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
(Trans-4-pentylcyclohexyl) ethyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2- (trans-4-propylcyclohexyl) ethyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2- (trans-4-pentylcyclohexyl) ethyl] naphthalene

Trans-4'-propyl-trans-4
-[2- (2-trifluoromethoxynaphthalene-6-
Yl) ethyl] bicyclohexane trans-4′-pentyl-trans-4- [2- (2
-Trifluoromethoxynaphthalen-6-yl) ethyl] bicyclohexane trans-4'-propyl-trans-4- [2- (1
-Fluoro-2-trifluoromethoxynaphthalene-6
-Yl) ethyl] bicyclohexane trans-4'-pentyl-trans-4- [2- (1
-Fluoro-2-trifluoromethoxynaphthalene-6
-Yl) ethyl] bicyclohexane trans-4'-propyl-trans-4- [2-
(1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) ethyl] bicyclohexane trans-4′-pentyl-trans-4- [2-
(1,3-Difluoro-2-trifluoromethoxynaphthalen-6-yl) ethyl] bicyclohexane

2-trifluoromethoxy-6- [2-
[4- (trans-4-propylcyclohexyl) phenyl] ethyl] naphthalene 2-trifluoromethoxy-6- [2- [4- (trans-4-pentylcyclohexyl) phenyl] ethyl]
Naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
[4- (trans-4-propylcyclohexyl) phenyl] ethyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
[4- (trans-4-pentylcyclohexyl) phenyl] ethyl] naphthalene 2-trifluoromethoxy-6- [2- [3,5-difluoro-4- (trans-4-propylcyclohexyl) phenyl] ethyl] naphthalene 2 -Trifluoromethoxy-6- [2- [3,5-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] ethyl] naphthalene

1-fluoro-2-trifluoromethoxy-6- [2- [3,5-difluoro-4- (trans-
4-propylcyclohexyl) phenyl] ethyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
[3,5-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] ethyl] naphthalene

Example 4 Synthesis of 1-fluoro-2-trifluoromethoxy-6- (trans-4′-vinylbicyclohexane-4-trans-yl) naphthalene

A Wittig reagent was prepared from methoxymethyltriphenylphosphonium chloride and potassium t-butoxide in THF under ice cooling. To this transformer-4'-
(1-Fluoro-2-trifluoromethoxynaphthalen-6-yl) bicyclohexane-4-one (This compound is obtained by converting a Grignard reagent prepared from 1-fluoro-6-bromo-2-trifluoromethoxynaphthalene to bicyclohexane- Reaction with 4,4'-dione monoethylene acetal, similarly dehydration, catalytic reduction, and deacetalization with formic acid) was added dropwise at 0 ° C.
After reacting for 1 hour, the temperature was returned to room temperature, water was added, and the organic layer was concentrated. Hexane was added for dissolution, and the insoluble triphenylphosphine oxide was filtered off.
Washed with the mixed solvent of No. 1. The crude product obtained by concentrating the hexane layer was dissolved in ethanol, an ethanol solution of potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Water was added, neutralized with dilute hydrochloric acid, and extracted with toluene. The organic layer was washed with water, dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain trans-4 ′-(1-fluoro-2-trifluoromethoxynaphthalen-6-yl) bicyclohexane-trans-4-. Crystals of carbaldehyde were obtained. A Wittig reagent prepared from methoxymethyltriphenylphosphonium iodide and potassium t-butoxide was similarly reacted therewith to give 1-fluoro-2-trifluoromethoxy-6- (trans-4'-vinylbicyclohexane-trans -4-yl) naphthalene was obtained.

In the same manner, the following compound is obtained.

2-trifluoromethoxy-6- (trans-4'-vinylbicyclohexane-4-trans-yl) naphthalene 2-trifluoromethoxy-6- [trans-4'-
(3-buten-1-yl) bicyclohexane-6-trans-4-yl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [trans-4 ′-(3-buten-1-yl) bicyclohexane -Trans-4-yl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(Trans-4′-vinylbicyclohexane-4-trans-yl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[Trans-4 '-(3-buten-1-yl) bicyclohexane-4-trans-yl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- (trans-4'-vinylbi Cyclohexane-4
-Trans-yl) naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- [trans-4 '-(3-buten-1-yl) bicyclohexane-4-trans-yl] naphthalene

2-trifluoromethoxy-6- (trans-4-vinylcyclohexyl) naphthalene 2-trifluoromethoxy-6- [trans-4- (3
-Buten-1-yl) cyclohexyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- (trans-4-vinylcyclohexyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- [trans-4- (3 -Buten-1-yl) cyclohexyl]
Naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(Trans-4-vinylcyclohexyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[Trans-4- (3-buten-1-yl) cyclohexyl] naphthalene

Example 5 Synthesis of 1-fluoro-2-trifluoromethoxy-6- (4-propylphenyl) naphthalene

34 g of 4-propylphenylboric acid (this compound is obtained by reacting a Grignard reagent prepared from 1-bromo-4-propylbenzene with trimethyl borate,
Then hydrolyzed with hydrochloric acid) and 25.5 g of 6-bromo-2-naphthol were dissolved in 92 mL of toluene, 46 mL of ethanol and 92 mL of water,
25.5 g of potassium carbonate and 1.3 mg of tetrakistriphenylphosphine palladium (0) were added, and the mixture was added at 75 ° C for 7 days.
Allowed to stir for hours. Water and toluene were added, and dilute hydrochloric acid was further added until the aqueous layer became weakly acidic. Extract with toluene,
The organic layers were combined, washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure to give 6-
(4-propylphenyl) naphthalen-2-ol 4
1.4 g were obtained. 12.7 g of the 6- (4-propylphenyl) naphthalen-2-ol was added to 50 m of dichloromethane.
L, and 13.1 g of N-fluoro-5-trifluoromethoxypyridinium-2-sulfonate was added, followed by stirring at room temperature for 18 hours. The oily substance obtained by post-treatment as described above was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1) to give 1
10 g of -fluoro-6- (4-propylphenyl) naphthalen-2-ol was obtained. Hereinafter, 1-fluoro-2-trifluoromethoxy-6- (4-propylphenyl) naphthalene was obtained by converting to S-ethyl dithiocarbonate and trifluoromethoxylating in the same manner as in Example 1.
3 g were obtained.

Example 6 1,3-Difluoro-2-
Trifluoromethoxy-6- (4-propylphenyl)
Synthesis of naphthalene

7.3 g of 4-propylphenylboric acid and 1,3-difluoro-trifluoromethanesulfonic acid
2-trifluoromethoxynaphthalen-6-yl 11 g
(This compound was obtained by triflating 1,3-difluoro-2-trifluoromethoxynaphthalen-6-ol with trifluoromethanesulfonic anhydride.)
Was dissolved in 50 mL of DMF, 0.4 g of tetrakistriphenylphosphine palladium (0) was added, and the mixture was stirred at 85 ° C. for 8 hours. Water and toluene were added, the aqueous layer was extracted with toluene, and the organic layers were combined, washed with water and then with saturated saline, and dried over anhydrous sodium sulfate. The oil obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1), and further recrystallized from ethanol to give 1,3-difluoro-2-triethyl. 6.3 g of crystals of fluoromethoxy-6- (4-propylphenyl) naphthalene were obtained.

Example 7 Synthesis of 1-fluoro-2-trifluoromethoxy-6- (2-fluoro-4-propylphenyl) naphthalene

In Example 5, 2-fluoro-4-propylphenylboric acid was used in place of 4-propylphenylboric acid, and in the same manner as in Example 5, except that 1-fluoro-2-trifluoromethoxy-6- ( 2-Fluoro-4-propylphenyl) naphthalene was obtained.

The following compounds were obtained in the same manner as in Example 5, 6 or 7.

2-trifluoromethoxy-6- (4-protylphenyl) naphthalene 2-trifluoromethoxy-6- (4-pentylphenyl) naphthalene 2-trifluoromethoxy-6- (4-heptylphenyl) naphthalene 1 -Fluoro-2-trifluoromethoxy-6- (4-
Pentylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- (4-
Heptylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(3-Buten-1-yl) phenyl] naphthalene

1,3-difluoro-2-trifluoromethoxy-6- (4-pentylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6
(4-heptylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (3-Buten-1-yl) phenyl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- (4-pentylphenyl) naphthalene 1,3,8-trifluoro-2- Trifluoromethoxy-6- (4-heptylphenyl) naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- [4- (3-buten-1-yl) phenyl] naphthalene

2-trifluoromethoxy-6- (2-fluoro-4-protylphenyl) naphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
Pentylphenyl) naphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
Heptylphenyl) naphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
(3-Buten-1-yl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- (2-
Fluoro-4-pentylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- (2-
Fluoro-4-heptylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (3-buten-1-yl) phenyl] naphthalene

2-trifluoromethoxy-6- (2,6
-Difluoro-4-propylphenyl) naphthalene 2-trifluoromethoxy-6- (2,6-difluoro-4-pentylphenyl) naphthalene 2-trifluoromethoxy-6- (2,6-difluoro-4-heptylphenyl) Naphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (3-buten-1-yl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- (2
6-difluoro-4-propylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-pentylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-heptylphenyl) naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (3-buten-1-yl) phenyl] naphthalene

1,3-difluoro-2-trifluoromethoxy-6- (2-fluoro-4-propylphenyl)
Naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-Fluoro-4-pentylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-Fluoro-4-heptylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2-Fluoro-4- (3-buten-1-yl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2,6-difluoro-4-propylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6
(2,6-difluoro-4-pentylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6
(2,6-difluoro-4-heptylphenyl) naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2,6-difluoro-4- (3-buten-1-yl)
Phenyl] naphthalene

2-trifluoromethoxy-6- [4-
(Trans-4-ethylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Propylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Butylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Pentylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-ethylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-propylcyclohexyl) phenyl]
Naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-butylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-pentylcyclohexyl) phenyl]
Naphthalene

1,3-difluoro-2-trifluoromethoxy-6- [4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (trans-4-butylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (trans-4-pentylcyclohexyl) phenyl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- [4- (trans-4-ethylcyclohexyl)
Phenyl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- [4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6 -[4- (trans-4-butylcyclohexyl)
Phenyl] naphthalene 1,3,8-trifluoro-2-trifluoromethoxy-6- [4- (trans-4-pentylcyclohexyl) phenylnaphthalene

2-trifluoromethoxy-6- [2-fluoro-4- (trans-4-ethylcyclohexyl)
Phenyl] naphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
(Trans-4-propylcyclohexyl) phenyl]
Naphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
(Trans-4-butylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
(Trans-4-pentylcyclohexyl) phenyl]
Naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (trans-4-butylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (trans-4-pentylcyclohexyl) phenyl] naphthalene

1,3-Difluoro-2-trifluoromethoxy-6- [2-fluoro-4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2-Fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2-Fluoro-4- (trans-4-butylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2-Fluoro-4- (trans-4-pentylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 2-trifluoro Methoxy-6- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-butylcyclohexyl) phenyl ] Naphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] naphthalene

1-fluoro-2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (trans-4-butylcyclohexyl) phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-Difluoro-4- (trans-4-ethylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-Difluoro-4- (trans-4-butylcyclohexyl) phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] naphthalene

2-trifluoromethoxy-6- [4-
[2- (Trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 2-trifluoromethoxy-6- [4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl]
Naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
[2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
[2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene

2-trifluoromethoxy-6- [2-fluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
[2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2-Fluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2-Fluoro-4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene

2-trifluoromethoxy-6- [2,6
-Difluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- [2- (trans-4-pentylcyclohexyl) ethyl ] Phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2,6-difluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] phenyl] naphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2,6-Difluoro-4- [2- (trans-4-pentylcyclohexyl) ethyl] phenyl] naphthalene

4'-ethyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-propyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-butyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-pentyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 4 '-(3-buten-1-yl) -4- (2 -Trifluoromethoxynaphthalen-6-yl) biphenyl

4'-ethyl-4- (1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl) biphenyl 4'-propyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-butyl-4- (1-fluoro-2-trifluoro Methoxynaphthalen-6-yl) biphenyl 4'-pentyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 4 '-(3-buten-1-yl) -4- (1- Fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

4'-Ethyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-propyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalene- 6-yl) biphenyl 4'-butyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 4'-pentyl-4- (1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl) biphenyl 4 '-(3-buten-1-yl) -4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

2'-fluoro-4'-ethyl-4- (2
-Trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-propyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-butyl-4- (2 -Trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-pentyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4 '-(3-butene-1 -Il) -4
-(2-trifluoromethoxynaphthalen-6-yl)
Biphenyl

2'-fluoro-4'-ethyl-4- (1
-Fluoro-2-trifluoromethoxynaphthalene-6
-Yl) biphenyl 2'-fluoro-4'-propyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-butyl-4- (1-fluoro-
2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-pentyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4 '-( 3-buten-1-yl) -4
-(1-Fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

2'-fluoro-4'-ethyl-4-
(1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-propyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-butyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4'-pentyl-4- (1,3-difluoro- 2-trifluoromethoxynaphthalen-6-yl) biphenyl 2'-fluoro-4 '-(3-buten-1-yl)-
4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

3,5-difluoro-4'-ethyl-4-
(2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4'-propyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4'-butyl- 4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4'-pentyl-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4'- (3-buten-1-yl)
-4- (2-trifluoromethoxynaphthalen-6-yl) biphenyl

3,5-difluoro-4'-ethyl-4-
(1-Fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4'-propyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5 -Difluoro-4'-butyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl)
Biphenyl 3,5-difluoro-4'-pentyl-4- (1-fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4 '-(3-buten-1-yl)
-4- (1-Fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

3,5-difluoro-4'-ethyl-4-
(1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3,5-difluoro-4′-propyl-4- (1,3-
Difluoro-2-trifluoromethoxynaphthalene-6
-Yl) biphenyl 3,5-difluoro-4'-butyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalene-6
Yl) biphenyl 3,5-difluoro-4′-pentyl-4- (1,3-
Difluoro-2-trifluoromethoxynaphthalene-6
-Yl) biphenyl 3,5-difluoro-4 '-(3-buten-1-yl)
-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

3-Fluoro-4'-ethyl-4- (6-
Trifluoromethoxynaphthalen-2-yl) biphenyl 3-fluoro-4'-propyl-4- (6-trifluoromethoxynaphthalen-2-yl) biphenyl 3-fluoro-4'-butyl-4- (6-trifluoro (Methoxynaphthalen-2-yl) biphenyl 3-difluoro-4'-pentyl-4- (6-trifluoromethoxynaphthalen-2-yl) biphenyl 3-fluoro-4 '-(3-buten-1-yl) -4 −
(6-trifluoromethoxynaphthalen-2-yl) biphenyl

3-Fluoro-4'-ethyl-4- (1-
Fluoro-2-trifluoromethoxynaphthalene-6
Yl) biphenyl 3-fluoro-4′-propyl-4- (1-fluoro-
2-trifluoromethoxynaphthalen-6-yl) biphenyl 3-fluoro-4'-butyl-4- (1-fluoro-2
-Trifluoromethoxynaphthalen-6-yl) biphenyl 3-difluoro-4'-pentyl-4- (1-fluoro-
2-trifluoromethoxynaphthalen-6-yl) biphenyl 3-fluoro-4 '-(3-buten-1-yl) -4-
(1-Fluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

3-Fluoro-4'-ethyl-4- (1,
3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3-fluoro-4'-propyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3-fluoro- 4'-butyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl)
Biphenyl 3-fluoro-4'-pentyl-4- (1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl 3-fluoro-4 '-(3-buten-1-yl) -4-
(1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl) biphenyl

Example 8 Synthesis of 1-fluoro-2-trifluoromethoxy-6- (4-propylphenyl) ethynylnaphthalene

4-propyl-1-ethynylbenzene 10
g, and 19.5 g of 2-bromo-5-fluoro-6-trifluoromethoxynaphthalene were dissolved in 50 mL of N, N-dimethylformamide (DMF), and copper (I) iodide 50 was dissolved.
mg and tetrakistriphenylphosphine palladium
(0) 100 mg was added, and the mixture was stirred at room temperature for 5 hours. Toluene was added, insolubles were filtered off, and the mixture was washed with water and saturated saline. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1),
Further recrystallization from ethanol gave 1-fluoro-2-
Trifluoromethoxy-6- (4-propylphenyl)
8.6 g of ethynylnaphthalene crystals were obtained.

The following compounds are obtained in the same manner.

2-trifluoromethoxy-6- (4-ethylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (4-propylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (4-butylphenyl) ethynyl Naphthalene 2-trifluoromethoxy-6- (4-pentylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- [4- (3-butene-
1-yl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (4-
Ethylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (4-
Butylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (4-
(Pentylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(3-Buten-1-yl) phenyl] ethynylnaphthalene

1,3-difluoro-2-trifluoromethoxy-6- (4-ethylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6
(4-propylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(4-butylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(4-pentylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (3-Buten-1-yl) phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
Ethylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
Propylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
Butylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2-fluoro-4-
(Pentylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- [2-fluoro-4-
(3-Buten-1-yl) phenyl] ethynylnaphthalene

1-fluoro-2-trifluoromethoxy-6- (2-fluoro-4-ethylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2-
Fluoro-4-propylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2-
Fluoro-4-butylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2-
Fluoro-4-pentylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [2-
Fluoro-4- (3-buten-1-yl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-fluoro-4-ethylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-fluoro-4-propylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-fluoro-4-butylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2-fluoro-4-pentylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2-Fluoro-4- (3-buten-1-yl) phenyl] ethynylnaphthalene

2-trifluoromethoxy-6- (2,6
-Difluoro-4-ethylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2,6-difluoro-4-propylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2,6-difluoro-4-butyl Phenyl) ethynylnaphthalene 2-trifluoromethoxy-6- (2,6-difluoro-4-pentylphenyl) ethynylnaphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (3-butene-1- Yl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-ethylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-propylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-butylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- (2,
6-difluoro-4-pentylphenyl) ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (3-buten-1-yl) phenyl] ethynylnaphthalene

1,3-difluoro-2-trifluoromethoxy-6- (2,6-difluoro-4-ethylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6
(2,6-difluoro-4-propylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2,6-difluoro-4-butylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
(2,6-difluoro-4-pentylphenyl) ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-difluoro-4- (3-buten-1-yl)
Phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Propylcyclohexyl) phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Butylcyclohexyl) phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- [4- (trans-4
-Pentylcyclohexyl) phenyl] ethynylnaphthalene

1-fluoro-2-trifluoromethoxy-6- [4- (trans-4-propylcyclohexyl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-butylcyclohexyl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [4-
(Trans-4-pentylcyclohexyl) phenyl]
Ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (Trans-4-propylcyclohexyl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (Trans-4-butylcyclohexyl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[4- (trans-4-pentylcyclohexyl) phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] ethynylnaphthalene 2-trifluoromethoxy- 6- [2,6-difluoro-4- (trans-4-butylcyclohexyl) phenyl] ethynylnaphthalene 2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] Ethynylnaphthalene

1-fluoro-2-trifluoromethoxy-6- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [2 ,
6-difluoro-4- (trans-4-butylcyclohexyl) phenyl] ethynylnaphthalene 1-fluoro-2-trifluoromethoxy-6- [2,
6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6-
[2,6-Difluoro-4- (trans-4-propylcyclohexyl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2,6-difluoro-4- (trans-4-butylcyclohexyl) phenyl] ethynylnaphthalene 1,3-difluoro-2-trifluoromethoxy-6
[2,6-difluoro-4- (trans-4-pentylcyclohexyl) phenyl] ethynylnaphthalene

Example 9 4-Pentylbenzoic acid-1
-Fluoro-2-trifluoromethoxynaphthalene-6-
Synthesis of IL

10.2 g of 4-pentylbenzoic acid chloride
And 10 g of 1-fluoro-6-trifluoromethoxynaphthalen-2-ol (this compound is 1-fluoro-2
-Reacting trifluoro-6-bromonaphthalene with magnesium to make a Grignard reagent, and reacting with trimethyl borate to form an arylboronic acid derivative;
This was obtained by oxidation with hydrogen peroxide. ) Was dissolved in 50 mL of dichloromethane, and 29 mL of pyridine was added.
Stirred at room temperature for 1 hour. Water and toluene were added, and the toluene layer was washed successively with diluted hydrochloric acid, water, and saturated saline. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1), and further recrystallized from ethanol to give 4-pentylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalene-6-. 13.4 g of il crystals were obtained.

Example 10 Synthesis of 1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-propyl) cyclohexylbenzoate

In Example 9, 4- (trans-4-propyl) cyclohexylbenzoic acid chloride was used in place of 4-pentylbenzoic acid chloride, and otherwise the same as in 4- (trans-4-propyl) cyclohexyl chloride. 1-Fluoro-2-trifluoromethoxynaphthalen-6-yl benzoate was obtained.

Example 11 Synthesis of 1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4-propylcyclohexylcarboxylate

In Example 9, 4-propylcyclohexylcarboxylic acid chloride was used in place of 4-pentylbenzoic acid chloride. Naphthalen-6-yl was obtained.

Example 12 4- (trans-4-propylcyclohexyl) cyclohexylcarboxylic acid-1
-Fluoro-2-trifluoromethoxynaphthalene-6-
Synthesis of IL

In Example 9, 4-propylcyclohexylcarboxylic acid chloride was used in place of 4-pentylbenzoic acid chloride, and the other conditions were the same as above, except that 4- (trans-4-propylcyclohexyl) cyclohexylcarboxylic acid-1- Fluoro-2-trifluoromethoxynaphthalen-6-yl was obtained.

The following compounds are obtained in the same manner.

4-Propylbenzoic acid-1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl 4-butylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4-heptylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (3-buten-1-yl) benzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4-propylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- Butylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4-pentylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4-heptylbenzoic acid-1, 3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- (3-buten-1-yl) benzoic acid-1,3-difluoro-2-t Trifluoromethoxynaphthalen-6-yl

2-fluoro-4-propylbenzoic acid-1
-Fluoro-2-trifluoromethoxynaphthalene-6-
Yl 2-fluoro-4-butylbenzoic acid-1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl 2-fluoro-4-pentylbenzoic acid-1-fluoro-2
-Trifluoromethoxynaphthalen-6-yl 2-fluoro-4-heptylbenzoic acid-1-fluoro-2
-Trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (3-buten-1-yl) benzoic acid-1-fluoro-2-trifluoromethoxynaphthalene-
6-yl 2-fluoro-4-propylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-butylbenzoic acid-1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl 2-fluoro-4-pentylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-heptylbenzoic acid-1,3-difluoro-2-tri Fluoromethoxynaphthalen-6-yl 2-fluoro-4- (3-buten-1-yl) benzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl

1,6-Difluoro-4-propylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-butylbenzoic acid-1-fluoro-2-trifluoromethoxy Naphthalen-6-yl 2,6-difluoro-4-pentylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-heptylbenzoic acid-1-fluoro-2-tri Fluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (3-buten-1-yl) benzoate-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-propyl Benzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-butylbenzoic acid-1,3-difluoro 2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-pentylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-heptylbenzoic acid 1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (3-buten-1-yl) benzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalene-6 -Ill

4- (trans-4-ethyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-butyl) cyclohexylbenzoic acid-1-fluoro-2-tri Fluoromethoxynaphthalene-
6-yl 4- (trans-4-pentyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-ethyl) cyclohexylbenzoic acid-1,3-difluoro-2 -Trifluoromethoxynaphthalen-6-yl 4- (trans-4-propyl) cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-butyl) cyclohexylbenzoic acid 1,3-Difluoro-2-trifluoromethoxynaphthalen-6-yl 1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-pentyl) cyclohexylbenzoate

2-fluoro-4- (trans-4-ethyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-propyl) cyclohexylbenzoic acid 1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-butyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro- 4- (trans-4-pentyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-ethyl) cyclohexylbenzoic acid-1,3-difluoro- 2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-propyl Cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-butyl) cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalene- 6-yl-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-pentyl) cyclohexylbenzoate

2,6-difluoro-4- (trans-4
-Ethyl) cyclohexylbenzoic acid-1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-propyl)
Cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-butyl) cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalene-6- Yl 2,6-difluoro-4- (trans-4-pentyl)
Cyclohexylbenzoic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-ethyl) cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalene- 6-yl 2,6-difluoro-4- (trans-4-propyl)
Cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-butyl) cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl 2,6-difluoro-4- (trans-4-pentyl)
Cyclohexylbenzoic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl

4-propylcyclohexylcarboxylic acid
1-fluoro-2-trifluoromethoxynaphthalene-6
-Yl 4-butylcyclohexylcarboxylic acid-1-fluoro-2
-Trifluoromethoxynaphthalen-6-yl 4-heptylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (3-buten-1-yl) cyclohexylcarboxylic acid-1-fluoro-2 -Trifluoromethoxynaphthalen-6-yl 4-propylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4-butylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl 4-pentylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4-heptylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalene-6- Yl 4- (3-buten-1-yl) cyclohe Shirukarubon acid 1,3-difluoro-2-trifluoromethoxy-6-yl

2-fluoro-4-propylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-butylcyclohexylcarboxylic acid-
1-fluoro-2-trifluoromethoxynaphthalene-6
-Yl 2-fluoro-4-pentylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalene-
6-yl 2-fluoro-4-heptylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalene-
6-yl 2-fluoro-4- (3-buten-1-yl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-propylcyclohexylcarboxylic acid-1,3 -Difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-butylcyclohexylcarboxylic acid-
1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-pentylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4-heptyl Cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (3-buten-1-yl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl

2,6-difluoro-4-propylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-butylcyclohexylcarboxylic acid-1-fluoro-2-trioxy Fluoromethoxynaphthalen-6-yl 2,6-difluoro-4-pentylcyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-heptylcyclohexylcarboxylic acid-1-fluoro -2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (3-buten-1-yl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6- Difluoro-4-propylcyclohexylcarboxylic acid-1,3-difluoro-2 Trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-butylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-pentylcyclohexylcarboxylic acid- 1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4-heptylcyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro -1,3-Difluoro-2-trifluoromethoxynaphthalen-6-yl-4- (3-buten-1-yl) cyclohexylcarboxylic acid

4- (Trans-4-ethylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-butylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2 -Trifluoromethoxynaphthalen-6-yl 4- (trans-4-pentylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-ethylcyclohexyl) cyclohexylcarboxylic acid 1,3-Difluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-propylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- ( Trans-4-butyl ester Clohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 4- (trans-4-pentylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalene-6 -Ill

2-Fluoro-4- (trans-4-ethylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-propylcyclohexyl) cyclohexyl Carboxylic acid-1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-butylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4 -Pentylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-
Trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-ethylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-
2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-propylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (Trans-4-butylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-
2-trifluoromethoxynaphthalen-6-yl 2-fluoro-4- (trans-4-pentylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl

2,6-difluoro-4- (trans-4
-Ethylcyclohexyl) cyclohexylcarboxylic acid-
1-fluoro-2-trifluoromethoxynaphthalene-6
-Yl 2,6-difluoro-4- (trans-4-propylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-butyl Cyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans-4-pentylcyclohexyl) cyclohexylcarboxylic acid-1-fluoro-2-trifluoromethoxynaphthalene -6-yl 2,6-difluoro-4- (trans-4-ethylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl 2,6-difluoro-4- (trans -4-propylcyclohexyl) cyclohexylca 1,3-Difluoro-2-trifluoromethoxynaphthalen-6-yl bonate 2,3-difluoro-4- (trans-4-butylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxy Naphthalen-6-yl 2,6-difluoro-4- (trans-4-pentylcyclohexyl) cyclohexylcarboxylic acid-1,3-difluoro-2-trifluoromethoxynaphthalen-6-yl

Example 13 Preparation of Liquid Crystal Composition General-purpose n-type host liquid crystal (H)

[0184]

Embedded image (The cyclohexane ring is in the trans configuration) is 72.5
It shows a nematic phase below ℃. This (H) has a cell thickness of 8.
A liquid crystal element was prepared by filling a TN cell of 0 μm. The physical properties and electro-optical properties were measured and were as follows.

Dielectric Anisotropy (Δε) -1.3 Refractive Index Anisotropy (Δn) 0.085 Next, (H) 80% and (I−
1)

[0186]

Embedded image Nematic liquid crystal composition (M-
As a result of preparing 1), the maximum liquid crystal phase temperature (T _NI ) was 7
7.2 ° C and 4 ° C or more. This (M-1) is calculated as 15
It was left at 0 ° C. for 20 hours. After cooling, the T _NI was measured, but it was 77.1 ° C., showing little change from before heating. Irradiation with ultraviolet light (1200 W / m ² ) for 20 hours showed no change in T _NI .
This (M-1) was allowed to stand at -20 ° C for 2 weeks, but no crystal precipitation or phase separation was observed. Next, the mixture was cooled to -60 ° C for crystallization and its melting point ( _TCN ) was measured to be -1 ° C.

Next, a cell was filled in the same manner as in (M-1) to prepare a liquid crystal element, and its electro-optical characteristics were measured. The results were as follows. Nematic phase maximum temperature (T _NI ) 77.2 ° C. Dielectric anisotropy (Δε) 1.6 Threshold voltage (Vth) 2.60 V Response time (τ) 30.0 ms Refractive index anisotropy (Δn) 0. [091] Here, the response time is a response time at the time of voltage application in which the rise time (? R) and the fall time (? D) are equal. The host liquid crystal (H) does not respond because it is n-type,
In (M-1), the dielectric anisotropy (Δε) is increased to 1.6 by adding 20% of (I-1), and 30.0%
High-speed response of m seconds has become possible. Further, it can be seen that the refractive index anisotropy (Δn) has also increased. When the voltage holding ratio of this device was measured, it showed a sufficiently high value both in the preparation and after the heating, similarly to the host liquid crystal (H).

(Comparative Example 1) 80% of the host liquid crystal (H) and a structure relatively similar to that of (I-1) but a 1-fluoro-2-cyanonaphthalene derivative (A)

[0189]

Embedded image A nematic liquid crystal composition (MA) consisting of 20% was prepared. A liquid crystal element was prepared in the same manner, and its electro-optical characteristics were measured. The results were as follows. Nematic phase maximum temperature (T _NI ) 78.9 ° C. Dielectric anisotropy (Δε) 3.2 Threshold voltage (Vth) 2.14 V Response time (τ) 40.0 ms Refractive index anisotropy (Δn) 0. 106 ( _MA ) has a slightly higher T _NI than (M-1)
Vth is low because ε is very large. However, it can be seen that the response time is as slow as 10 ms and does not reach (I-1). Further, when the voltage holding ratio of this device was measured, a considerable decrease was confirmed after heating as compared with the host liquid crystal (H).

As described above, the compound (I-1) is excellent in compatibility with other liquid crystal compounds, has a high maximum temperature of the nematic phase, and increases the dielectric anisotropy by adding the compound to improve the high-speed response. It is relatively similar to a conventionally known structure in that it has the features that it is possible to further increase the refractive index anisotropy, and that it has a high voltage holding ratio and can sufficiently drive an active matrix. It has better properties than the compound of A).

[0191]

The compound represented by the general formula (I) according to the present invention can be easily produced industrially as shown in Examples, and is chemically stable to heat, light, water and the like. It is. In addition, it has excellent liquid crystal properties and excellent compatibility with currently used liquid crystal compounds or compositions. Further, the addition thereof has the advantages that the dielectric anisotropy can be greatly increased and the threshold voltage thereof can be reduced, and that the high-speed response and the anisotropy of the refractive index can be increased. Therefore, it is very useful and practical for preparing a liquid crystal composition which can be driven at a low voltage with a wide temperature range of a nematic phase, a low threshold voltage, and a high speed response.

Continued on the front page F term (reference) 4H006 AA01 AA02 AB64 AC13 AC26 AC43 AC48 BJ20 BJ50 BM10 BM30 BM71 BP20 BP30 BP60 BT24 BT26 BT34 BT36 KA14 KF10 4H027 BA01 BB03 BB04 BC03 BC04 BD01 BD02 BD03 BD05 BD02 BD03 BD03

Claims (8)

[Claims] 1. A compound of the general formula (I) (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkoxylalkyl group, an alkenyl group or an alkenyloxy group.
May be substituted with one or two or more fluorine atoms, and ring A is trans-1,
4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, and 2,6-difluoro-1,4 which may be substituted by one or more fluorine atoms -Phenylene group, pyridine-2,5-
Diyl group, pyrimidine-2,5-diyl group, pyrazine-
Represents a 2,5-diyl group, a pyridazine-3,6-diyl group, a trans-1,3-dioxane-2,5-diyl group or a decahydronaphthalene-3,8-diyl group, and ring B is trans-1 1,4-cyclohexylene group, which may be substituted by one or more fluorine atoms,
4-phenylene group, 2-fluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2 , 5-diyl group, pyridazine-3,6
-Diyl group, trans-1,3-dioxane-2,5-
Represents a diyl group, a decahydronaphthalene-3,8-diyl group or a single bond, and L and M are each independently —CH _{2
CH 2 -, - CH 2 O} -, - OCH 2 -, - COO -, -
_{OCO -, - CF 2 O -} , - OCF 2 -, - CH 2 CH 2 C
H ₂ CH ₂ —, —CF ＝ CF—, —C≡C— or a single bond. When ring B represents a single bond, M represents a single bond.
X ^{1 to} X ³ each independently represent a hydrogen atom or a fluorine atom. )). 2. The liquid crystalline compound according to claim 1, wherein in formula (I), X ² represents a fluorine atom. 3. The method according to claim 1, wherein in formula (I), L and M each independently represent —CH ₂ CH ₂ —, —COO—, —C≡C— or a single bond. Liquid crystalline compounds. 4. The liquid crystalline compound according to claim 1, wherein at least one of L and M in the general formula (I) represents a single bond. 5. The method according to claim 1, wherein in the general formula (I), R represents a linear alkyl group having 1 to 7 carbon atoms.
The liquid crystal compound according to 2, 3 or 4. 6. A compound of the general formula (IIa) (Wherein, X ^{1 to} X ³ each independently represent a hydrogen atom or a fluorine atom, and Wa represents ^a chlorine atom, a bromine atom or an iodine atom). The method for producing a compound represented by the general formula (I) according to claim 1, wherein the compound is used. 7. A liquid crystal composition comprising the liquid crystal compound represented by the general formula (I) according to claim 1. 8. A liquid crystal device comprising the liquid crystal composition according to claim 7 as a constituent.