JP2000355560A - New liquid-crystalline compound of 2-fluoronaphthalene derivative, and liquid-crystalline composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound, having a fluorine atom as the polar group at the 6-site of naphthalene ring, low in viscosity, easily made high in voltage-holding capacity, and useful as a material for electrooptical liquid crystal displays. SOLUTION: This 2-fluoronaphthalene derivative is shown by the formula [R is a 1-20C (substituted)alkyl or the like; ring A is a single bond, trans-1,4- cyclohexylene or the like; L and M are each a single bond, ethylene or the like; and X1 to X5 are each H or F, wherein at least one of X1 to X3 is F], e.g. 6-(4-propylphenyl)-1,2-difluoronaphthalene. It is obtained by reacting 6- methoxynaphthalen-2-yl-boric acid with 4-propyliodobenzene, fluorinating the product with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(trifluoroborate) and bis-(2-methoxyethyl)aminosulfur trifluoride or the like, and finally reducing and dehydrofluorinating the above product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel liquid crystal compound having a 2-fluoronaphthyl group, a liquid crystal composition containing the same, and a liquid crystal display device using the same, which is useful as an electro-optical liquid crystal display material.

[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 often 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, it is a fact that these fluorine-based liquid crystal compounds alone cannot sufficiently satisfy the required characteristics of a liquid crystal composition which is becoming increasingly sophisticated year by year.

Other liquid crystal compounds having a chemical structure in which a fluorine atom is directly bonded to another kind of ring structure as a polar group are known. For example, a liquid crystal compound having a structure in which a fluorine atom is directly bonded to a cyclohexane ring has been reported (German Published Patent No. 3328638). However, the compound having such a structure is completely lacking in practicality because fluorine is easily eliminated to easily form a cyclohexene derivative.

On the other hand, a naphthalene ring is also known as an aromatic ring substituted by a polar group. For example, a liquid crystal compound having a 6-cyanonaphthyl group has already been reported (D. Coates
Cryst. Liq. Cryst., 37 249 (1976)), in which the 6-cyanonaphthyl group has a strong dielectric constant similar to the 4-cyanophenyl group and the 4′-cyanobiphenyl-4-yl group. It is shown to have anisotropy.

However, a liquid crystal compound such as a 2-fluoronaphthalene derivative having a fluorine atom as a polar group is hardly known, and examples in which a synthesis method is actually shown and specific physical property values are shown are as follows. Absent. Further, a material having a larger dielectric anisotropy has been demanded in order to meet the demand for a further lower voltage, and a liquid crystal material which is a 2-fluoronaphthalene derivative having a fluorine atom in a molecule has been further demanded. No such compound has ever been known.

[0010]

An object of the present invention is to provide a novel liquid crystal compound having a structure in which a fluorine atom is directly bonded to a 6-position of a naphthalene ring as a polar group. It is to provide a practical liquid crystal composition using the composition.

[0011]

The present invention has been made in order to solve the above problems. General formula (I)

[0012]

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[0013] (wherein, R represents an alkyl group, an alkoxyl group having 1 to 20 carbon atoms, alkoxyl group, an alkenyl group or alkenyloxy group which are C ₁
May be substituted with an alkoxyl group or one or more fluorine atoms -C _7, ring A is trans-1,4-cyclohexylene group, 1,4-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-diyl group, naphthalene-2,6
-Diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,
6-diyl group or a single bond, L and M are each independently _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 CH
_{2 -, - C (CH 3} ) CH -, - CHC (CH 3) - or represents a single bond, when the ring B represents a single bond M represents a single bond. X ^{1 to} X ⁵ each independently represent a hydrogen atom or a fluorine atom, and X ¹ , X ² and X ^{3 each} have at least one of
Represents a fluorine atom. A novel liquid crystalline compound which is a 2-fluoronaphthalene derivative represented by the following formula:

2. 2. The compound according to the above item 1, wherein ring A, L and M in formula (I) represent a single bond.

3. In the general formula (I), the above-mentioned 1 wherein ring A represents a trans-1,4-cyclohexylene group
A compound as described.

4. In the general formula (I), ring A is 1,4
-The compound according to the above 1, which represents a phenylene group.

5. In the general formula (I), the above 1 or 2 wherein at least one of L and M represents a single bond
Described compounds

6. 2. The compound according to the above 1, wherein in the general formula (I), ring A represents a 2-fluoro-1,4-phenylene group or 2,6-difluoro-1,4-phenylene group, and M represents a single bond.

[7] 1 to 4 wherein R represents a linear alkyl group having 1 to 7 carbon atoms in the general formula (I).
A compound as described.

[8] In the general formula (I), R represents a linear alkenyl group having 1 to 7 carbon atoms.
4. The compound according to 4.

9. A liquid crystal composition comprising the compound described in the general formula (I) according to the above 1.

10. 10. The liquid crystal composition according to the above item 9, which is used for driving an active matrix.

11. A liquid crystal element comprising the liquid crystal composition according to the above item 9 as a constituent element.

12. An active matrix driven liquid crystal display device using the liquid crystal composition according to the above item 10. Was found as a means for solving the above-mentioned problem.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been made in order to solve the above-mentioned problems.

[0026]

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A novel liquid crystalline compound which is a 2-fluoronaphthalene derivative represented by the following formula: In the formula, R is an alkyl group having 1 to 20 carbon atoms, an alkoxylalkyl group,
Or an alkenyl group, which may be substituted with a C ₁ -C ₇ alkoxyl group or at least one fluorine atom, preferably a linear group having 1 to 7 carbon atoms, More preferably, it is a group or an alkenyl group, and a linear alkyl group having 1 to 7 carbon atoms is particularly preferable. In the case of an alkenyl group, 3-butene-1
-Yl or trans-3-pentenyl is preferred. Ring A is a trans-1,4-cyclohexylene group,
1,4-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-diyl group, naphthalene-2,6-diyl group,
Represents a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or a decahydronaphthalene-2,6-diyl group or a single bond, usually a trans-1,4-cyclohexylene group, When a low viscosity is required, a single bond is preferable, when a high refractive index anisotropy (Δn) is required, a 1,4-phenylene group is preferable, and when a large dielectric anisotropy (Δε) is required. Is preferably a 2-fluoro-1,4-phenylene group or a 2,6-difluoro-1,4-phenylene group. L and M are each independently -CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH
_{2 -, - C (CH 3} ) CH -, - CHC (CH 3) - or a single bond, but if the ring B represents a single bond M represents a single bond, at least one of a single bond Is preferred. X
^{1 to} X ⁵ each independently represent a hydrogen atom or a fluorine atom, and at least one of X ¹ , X ² and X ³ represents a fluorine atom, but when high liquid crystallinity is required, X 1
¹ and X ³ and X ⁵ are preferably hydrogen atoms, and when a large Δε is required, it is preferable that at least one, and preferably two or more, of X ^{1 to} X ⁵ are fluorine atoms.

As described above, the compound of the general formula (I) can include a very wide variety of compounds depending on the selection of R, rings A, L, M and X ^{1 to} X ^5. In the above, each compound represented by the following general formulas (Iaa) to (Ipf) is preferable.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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In the above formula, R ¹ represents a linear alkyl group having 1 to 7 carbon atoms, and R ² represents an alkenyl group having 2 to 7 carbon atoms, particularly a vinyl group or 3-buten-1-yl. ,
Represents a trans-3-penten-1-yl group. further,
In the above formula, (Iaa), (Iab), (Iac), (Ia)
e), (Iaf), (Iag), (Iba), (Ib)
b), (Ibc), (Ibd), (Iea), (Ie)
c), (Iee), (Ieg), (Iej), (Ig)
a), (Igc), (Ige), (Igg), (Ia
Compounds b) and (Iac) are more preferred.

The compound (I) of the present invention has an R, a ring A,
It can be produced as follows according to L, M and X ^{1 to} X ⁵ .

[1] Formulas (Iaa) to (Ian),
Process for producing compounds represented by (Iea) to (Ies) and (Ina) to (Ink)

(I) Method for producing compound represented by general formula (Iaa) General formula (IIa)

[0045]

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(Wherein, R ¹ represents the above-mentioned meaning, and W ¹ represents a halogen atom such as chlorine, bromine or iodine, and preferably represents a bromine atom.) Or a lithiation reaction with an alkyllithium such as butyllithium to obtain an organometallic reactant, or the resulting metal reactant is used as a reactant such as zinc, copper or boron by metal exchange, and is represented by the general formula (I)
IIa)

[0047]

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(Wherein, Y ¹ represents a halogen atom such as bromine or iodine or a leaving group such as trifluoromethanesulfonyloxy group, and Z ¹ represents a phenolic hydroxyl group protected by a methoxy group or a benzyloxy group. With a transition metal catalyst such as tetrakistriphenylphosphine palladium (0) or tetrakistriphenylphosphinenickel (0) to give a compound of the general formula (IVa)

[0049]

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(Wherein R ¹ and Z ¹ have the same meanings as described above), and are deprotected with hydrobromic acid or the like to give a compound of the general formula (Va)

[0051]

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(Wherein, R ¹ represents the same meaning as described above). This naphthol derivative was treated with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octanebis (tetrafluoroborate), 1-fluoro-4-hydroxy-1,4-
Diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate), N-fluoro-pyridinium pyridine heptafluorodiborate, N-fluorobenzenesulfonimide, N-fluoro-5- (trifluoromethyl) pyridinium-2 -Sulfonate or bistetrafluoroborate N, N'-difluoro-
By reacting with a fluorinating agent such as 2,2'-bipyridinium, the compound represented by the general formula (VIa)

[0053]

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(Wherein R ¹ has the same meaning as described above), and this is a compound such as diethylaminosulfur trifluoride, bis- (2-methoxyethyl) aminosulfur trifluoride or sulfur tetrafluoride. The compound is further fluorinated with a fluorinating agent,

[0055]

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(Wherein R ¹ represents the same meaning as described above), which is subjected to catalytic reduction using a transition metal catalyst such as palladium carbon and, if necessary, a base such as potassium t-butoxide. By dehydrofluorination, the compound represented by the aforementioned general formula (Iaa) can be produced.

(Ii) Method for producing compound represented by general formula (Iac) (Iaa) obtained by (i) in [1] is lithiated with butyllithium or the like to give 1-chloromethyl-4-fluoro- 1,4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate), 1-fluoro-
4-hydroxy-1,4-diazoniabicyclo [2.
2.2] octane bis (tetrafluoroborate),
N-fluoro-pyridinium pyridine heptafluorodiborate, N-fluorobenzenesulfonimide,
By reacting with a fluorinating agent such as N-fluoro-5- (trifluoromethyl) pyridinium-2-sulfonate or N, N'-difluoro-2,2'-bipyridinium bistetrafluoroborate, the compound represented by the general formula (Ia)
The compound represented by c) can be produced.

The formula (Iac) is represented by the formula (VIIIa)

[0059]

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Is reacted with a chlorinating agent such as thionyl chloride to form an acid chloride, and is reacted with ethylene gas in the presence of aluminum chloride to obtain (IXa)

[0061]

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The compound represented by the formula is obtained. Further, the general formula (IIa) is reacted with magnesium to give a Grignard reagent, or lithiated with an alkyl lithium such as butyl lithium to give an organometallic reagent, which is reacted with a compound represented by (IXa), Then, after dehydration in the presence of an acid catalyst, this was decomposed into 2,3-dichloro-5,6
-Dicyano-1,4-benzoquinone, chloranil, bromine or the like to give a compound of the formula (Ia)
The compound represented by c) can be produced.

(Iii) Formulas (Iaa) and (Ia)
Method for producing compound represented by b) In formula (I) of [1], general formula (IIIb) is used instead of general formula (IIIa)

[0064]

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(In the formula, Y ¹ and Z ¹ have the same meanings as described above.) In addition, in (ii), the compound represented by the general formula (VIIIb) is used in place of the compound represented by the formula (VIIIa). The compound represented by (Iab) can be produced.

In (ii) of [1], (VIII)
(VIIIb) instead of the compound represented by a)

[0067]

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A mixture of the compounds represented by the general formulas (Iaa) and (Iab) is obtained in the same manner except that the compound represented by the formula (Ia) is used. Further, the compound represented by the general formula (Iab) can be produced by purification by column chromatography or the like. Using this method, the general formula (I
The compound represented by aa) can be produced.

(Iv) Method for producing compounds represented by general formulas (Iaa) to (Iad) The general formula (IIa) is reacted with magnesium to obtain a Grignard reagent, or lithiated with alkyl lithium such as butyl lithium. To obtain an organolithium reactant, or a reactant such as an organozinc, an organocopper or an organoboron prepared by transmetallation from the obtained reactants, by the general formula (IIIc)

[0070]

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(Wherein Y ¹ and X ^{1 to} X ³ have the same meanings as described above) and a transition such as tetrakistriphenylphosphine palladium (0) or tetrakistriphenylphosphine nickel (0). By reacting in the presence of a metal catalyst, the compound of the general formula (Ia)
Compounds represented by a) to (Iad) can be produced.

(V) Formulas (Iae), (Iaj),
(Iea), (Iee), (Iej), (Iep),
Method for producing compounds represented by (Ier), (Ina), (Ine), (Ing) and (Inj) In (i) of [1], general formulas (IIb) to (IIb) are used instead of general formula (IIa). (IIk)

[0073]

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(In the formula, R ¹ and W ¹ have the same meanings as described above.)
The general formulas (Iae), (Iaj), (Iea), (Iee), (Iee)
ej), (Iep), (Ier), (Ina), (In)
e) The compounds represented by (Ing) and (Inj) can be produced.

(Vi) Formulas (Iaf), (Iak),
(Ieb), (Ief), (Iek) and (Inb)
Method for producing compound represented by formula (1) In (iii) of (1), compounds represented by formulas (IIb) to (IIf) and (IIj) are used in place of the compound represented by formula (IIa) Other than the above, general formulas (Iaf), (Iak), (Ieb), (Ie)
f), (Iek), (Ieq), (Ies) and (I
The compound represented by nb) can be produced.

(Vii) Formulas (Iag) and (Ia)
m), (Iec), (Ieg), (Iem), (Ie)
q), (Ies) and (Inc), (Inf), (I
nh), a method for producing a compound represented by (Ink) In (ii) of [1], instead of the general formula (IIa),
Except for using the compounds represented by the general formulas (IIb) to (IIj), the general formulas (Iaf), (Iak),
eb), (Ief), (Iek), (Ieq), (Ie)
The compounds represented by s) and (Inb) can be produced.

(Viii) Formulas (Iah) and (Ia)
n), (Ied), (Ieh), (Ien), (In)
d) and a process for producing the compound represented by (Ies) In the compound represented by (iv) in [1], the compound represented by the general formula (I)
In place of the compound represented by Ia), general formulas (IIb) to
Except for using the compounds represented by (IIf) and (IIj), the general formulas (Iah), (Ian), and (Ie)
d), (Ieh), (Ien), (Ind) and (I
es) can be produced.

[2] Method for producing compounds represented by general formulas (Iba) to (Ibf) and (Ifa) to (Ifk) In the method (1) of (i) and (ii),
In place of a), general formulas (IIo) to (IIv)

[0079]

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(In the formula, R ² and W ¹ have the same meanings as described above.)
In the same manner except that a compound represented by the formula (I) is used,
Compounds represented by ba) to (Ibf) and (Ifa) to (Ifk) can be produced.

[3] Method for producing compounds represented by formulas (Iga) to (Ign)

(I) Method for producing compound represented by general formula (Iga) General formula (IIId)

[0083]

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(Wherein W ¹ represents a halogen atom such as chlorine, bromine or iodine, preferably a bromine atom;
Z ¹ represents a phenolic hydroxyl group protected by a methoxy group or a benzyloxy group. ) Is reacted with magnesium to make a Grignard reactant, or lithiated with an alkyl lithium such as butyl lithium to make an organometallic reactant,
This is represented by the general formula (IXa)

[0085]

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(Wherein R ¹ has the same meaning as described above), and after dehydration and hydrogenation, if necessary, cis / trans isomerization of the cyclohexane ring is carried out. By deprotection, the compound represented by the general formula (Vb)

[0087]

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(Wherein, R ¹ has the same meaning as described above). By fluorinating this naphthol derivative in the same manner as in (1) [1], the compound represented by the aforementioned general formula (Iga) can be produced.

(Ii) Method for producing the compound represented by the general formula (Igc) In the same manner as in (ii) of [1] except that the general formula (Vb) is used instead of the general formula (Va). (Ig
The compound represented by c) can be produced.

(Iii) Formulas (Ige) and (Ig)
g), a method for producing compounds represented by (Igj) and (Igm) In (i) and (ii) of [3], the compound represented by the general formula (IX)
In place of a), general formula (IXb) or general formula (IXc)

[0091]

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(Wherein, R ¹ has the same meaning as described above) except that general formulas (Ige), (Igg) and
Compounds represented by (Igj) and (Igm) can be produced.

(Iv) Formulas (Igb) and (Ig
d), (Igf), (Igh), (Igk) and (I
gn) Production method of compound represented by general formula (IIIe)

[0094]

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(Wherein W ¹ represents a halogen atom such as chlorine, bromine or iodine, but preferably represents a bromine atom), by reacting a naphthalene derivative represented by the following formula with magnesium to obtain a Grignard reagent: Alternatively, an lithiation reaction with an alkyl lithium such as butyl lithium is performed to obtain an organolithium reactant, which is reacted with the general formula (IXa), (IXb) or (IXc), and dehydrated.
After hydrogenation, isomerization gives the general formula (Ige),
Compounds represented by (Igg), (Igj) and (Igm) can be produced.

[4] Method for producing compounds represented by general formulas (Ija) to (Ijn) In the process [3], the general formula (IXa) is replaced with the general formula (Ija)
Xd), (IXe) and (IXf)

[0097]

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Compounds represented by the general formulas (Ija) to (Ijn) can be produced in the same manner except that (wherein, R ¹ has the same meaning as described above).

[5] Formulas (Ica) to (Icj),
(Ika) to (Ikn) and (Ima) to (Imk)
In the production method of the compound represented by the formula (3), the general formula (Xa) is replaced with the general formula (Xa)
a) to (Xk)

[0100]

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(Wherein R ¹ has the same meaning as described above), except that isomerization is not carried out.
(Icj), (Ika) to (Ikn) and (Ima)
To (Imk).

[6] Method for producing compounds represented by formulas (Iha) to (Ihf) and (Ida) to (Idf)

(I) Formulas (Iha) and (Ih)
Method for producing compound represented by b) In (i) of [1], instead of the compound represented by the general formula (IXa), the compound represented by the general formula (IXg)

[0104]

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(Z ² represents a hydroxyl group protected by a protecting group such as a methoxy group or a benzyloxy group). The reaction is carried out in the same manner as described above, followed by deprotection and further oxidation. By the general formula (XIa)

[0106]

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(In the formula, X ^{1 to} X ³ have the same meanings as described above.)
Is obtained. In this formula (XIIa)

[0108]

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The compounds represented by (Iha) and (Ihb) wherein R ² is a vinyl group can be produced by reacting a Wittig reagent represented by the following formula:

The formula (XIa) is replaced by the formula (XIIb)

[0111]

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After reacting the Wittig reactant represented by the formula as many times as necessary, the Wittig reactant represented by the formula (XIIa) is reacted to obtain a general formula having R ² of various chain lengths. (Iha) and (Ihb)
Can be produced.

The compounds represented by the general formulas (Iha) and (Ihb) are the same as the compounds represented by the general formula (IX) in (i) of [1].
The same reaction is performed except that the compound represented by the general formula (IXg) is used instead of the compound represented by a), followed by deprotection and bromination with hydrobromic acid, phosphoric acid bromide, or the like. Or after chlorination with thionyl chloride or the like, the general formula (II)
w)

[0114]

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(Wherein R ¹ and W ³ have the same meanings as described above), by reacting the alkenyl halide with magnesium to obtain a Grignard reagent, or by lithiation with an alkyl lithium such as butyl lithium. The compounds represented by the general formulas (Iha) and (Ihb) can also be produced by reacting with an organometallic reactant in the presence of a transition metal catalyst.

(Ii) Formulas (Ihc) to (Ihf)
And methods for producing compounds represented by (Ida) to (Idf) In (i) of [6], general formulas (IXh) to (IXn) are used instead of general formula (IXg).

[0117]

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Compounds represented by the general formulas (Ihc) to (Ihf) and (Ida) to (Idf) can be produced in the same manner except that (Z ² has the same meaning as described above).

Representative examples of the compound represented by the general formula (I) thus produced are shown in Table 1.

[0120]

[Table 1]

(In the table, Cr indicates a crystal phase, and I indicates an isotropic liquid phase.)

Many of the compounds represented by the general formula (I) exhibit relatively excellent compatibility with other liquid crystal materials. When two or more fluorine atoms are introduced in the same direction with respect to the molecular axis, the polarity is large and the characteristics as a strong p-type liquid crystal are exhibited. In addition, the molecule does not contain a cyano group or an ester group,
When no ether oxygen is contained, it is easy to obtain a high specific resistance and a high voltage holding ratio. Therefore, it can be suitably used as a material for a liquid crystal display cell in a state of a mixture with another liquid crystal compound. The compound (I) can be used in any of the above-mentioned various display methods, but the TN of the simple matrix drive or the active matrix drive is used.
It is suitable for use in a type display element and an STN display element, and is particularly preferably used as a polar component of an active matrix driving liquid crystal material.

As described above, preferred examples of the nematic liquid crystal compound which can be used as a mixture with the compound represented by the general formula (I) include the first component in the composition provided by the present invention. At least one compound represented by the general formula (I), and as other components, it is particularly preferable to include at least one of the following second to fourth components.

That is, the second component is a so-called fluorine (halogen) p-type liquid crystal compound and has the following general formula (A)
1) to (A3).

[0125]

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In the above formula, R ^b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch and may be a 3- to 6-membered cyclic group. may have a structure, any -CH present in the group ₂ -
Is -O-, -CH = CH-, -CH = CF-, -CF =
CH—, —CF ＝ CF— or —C≡C— may be replaced, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group, A linear alkyl group of Formulas 2 to 7,
A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms
~ 5 alkyl groups are preferred. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring A, ring B and ring C are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group and at least one fluorine atom. 1,4-
Phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, fluorine atom A 1,4-cyclohexenylene group optionally substituted with 1,3
-Dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, but trans-1,4-cyclohexylene,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by a fluorine atom or 1,4-optionally substituted by one or two fluorine atoms Phenylene groups are preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-
When it is a 2,6-diyl group, ring A is trans-1,
It is preferably a 4-cyclohexylene group, and when ring C is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1 , 4-cyclohexylene. In (A3), ring A is preferably a trans-1,4-cyclohexylene group.

L ^a , L ^b and L ^c are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, -CF = CF-, -C≡C- or -CH = NN =
CH— represents a single bond, an ethylene group, a 1,4-butylene group, —COO—, —OCF ₂ —, —CF ₂ O—, or —CF.
＝ CF— or —C≡C— is preferred, and a single bond or an ethylene group is particularly preferred. In (A2), at least one of them preferably represents a single bond in (A3).

Ring Z is an aromatic ring represented by the following general formula (IX)
a) to (IXc).

[0130]

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In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom, and in (IXa),
At least one of Y ^a and Y ^b is preferably a fluorine atom, in (IXb), it is preferable that at least one Y ^d to Y ^f is a fluorine atom, in particular Y ^d is a fluorine atom Is more preferred.

[0132] end group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or a carbon atoms substituted by two or more fluorine atoms 2 or 3
Represents an alkoxyl group, an alkyl group, an alkenyl group or an alkenyloxy group, preferably a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group, and particularly preferably a fluorine atom.

In (A2), the compound of the general formula (I) of the present invention is excluded.

The third component is a so-called cyano-based p-type liquid crystal compound, which comprises compounds represented by the following formulas (B1) to (B3).

[0135]

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In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and may be a 3- to 6-membered cyclic group. may have a structure, any -CH present in the group ₂ -
Is -O-, -CH = CH-, -CH = CF-, -CF =
CH—, —CF ＝ CF— or —C≡C— may be replaced, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group, A linear alkyl group of Formulas 2 to 7,
A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms
~ 5 alkyl groups are preferred. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring D, ring E and ring F are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group and one or more fluorine atoms. 1,4-
Phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, fluorine atom A 1,4-cyclohexenylene group optionally substituted with 1,3
-Dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, but trans-1,4-cyclohexylene,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by a fluorine atom or 1,4-optionally substituted by one or two fluorine atoms Phenylene groups are preferred. In particular, when ring E is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-
When it is a 2,6-diyl group, ring D is trans-1,
It is preferably a 4-cyclohexylene group, and when ring F is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring D and ring E are trans-1 , 4-cyclohexylene. In (B3), ring D is preferably a trans-1,4-cyclohexylene group.

[0138] L ^d, L ^e and L ^f is a linking group, are independently a single bond, an ethylene group (-CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, - CF = CF -, - C≡C -, - OCH 2 -, - C
H ₂ O-, or represent a -CH = NN = CH-, a single bond, an ethylene _{group, -COO -, - OCF 2 -} , - CF 2 O
—, —CF ＝ CF— or —C≡C— is preferred, and a single bond, an ethylene group or —COO— is particularly preferred. In (B2), at least one of them is (B2)
In 3), at least two of them preferably represent a single bond.

Ring Y is an aromatic ring and has the following general formula (IX)
d) to (IXf).

[0140]

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In the formula, Y ^{h to} Y ⁿ each independently represent a hydrogen atom or a fluorine atom, and in (IXe),
Y ⁿ and Y ^o are preferably hydrogen atoms.

The terminal group Pa represents ^a cyano group (—CN), a cyanato group (—OCN) or —C≡CCN, preferably a cyano group.

In (B2), the compound of the general formula (I) of the present invention is excluded.

The fourth component has a dielectric anisotropy of about 0.
It is a so-called n-type liquid crystal, and has the following general formulas (C1) to (C
It consists of the compound shown in 3).

[0145]

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In the above formula, R ^d and R ^e each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch; may have a cyclic structure having 3 to 6-membered ring, any -CH ₂ present in the group - is -O -, - CH = CH-,
May be replaced by —CH ＝ CF—, —CF ＝ CH—, —CF ＝ CF— or —C≡C—, and any hydrogen atom present in the group is replaced by a fluorine atom or a trifluoromethoxy group , But may have 1 carbon atom
To 7 linear alkyl groups, 2 to 7 carbon atoms, linear 1
An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxyl group having 1 to 3 carbon atoms, or 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms. 5 to 5 linear alkyl groups are preferred,
Further, at least one is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or a linear 3-alkenyl group having 4 to 7 carbon atoms. Particularly preferred.

Ring G, ring H, ring I and ring J are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1-2 fluorine atoms. A 1,4-phenylene group which may be substituted by an atom or a methyl group, naphthalene-2 which may be substituted by one or more fluorine atoms,
6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene optionally substituted by 1 to 2 fluorine atoms Group, 1,3-dioxane-
Represents a trans-2,5-diyl group, a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, and in each compound, a trans-decahydronaphthalene-trans-2,6-diyl group; A naphthalene-2,6-diyl group which may be substituted by the above fluorine atom,
Tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans- 2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-
It is preferred that the number of 2,5-diyl groups is one or less, and the other rings are trans-1,4-cyclohexylene groups or 1,4, which may be substituted by one or two fluorine atoms or methyl groups. -Preferably a phenylene group.

L ^g , L ^h and L ⁱ are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, -CF = CF-, -C≡C- or -CH = NN =
It represents a CH-, single bond, ethylene group, 1,4-butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2
O-, -CF = CF-, -C≡C- or -CH = NN
ＣＨCH— is preferred, and in (C2), at least one of them preferably represents a single bond in (C3).

The compound of the general formula (I) of the present invention is excluded from (C2).

More preferred forms of (C1) can be represented by the following general formulas (C1a) to (C1h).

[0151]

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In the above formulas, R ^f and R ^g are each independently a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, and a carbon atom having 4 carbon atoms. -7 straight-chain 3-alkenyl group, C1-C3 straight-chain alkoxyl group or C1-C5 straight-chain alkyl substituted at the terminal with an alkoxyl group having 1-3 carbon atoms. Wherein at least one is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or a linear 3-alkenyl group having 4 to 7 carbon atoms. Represents However, when ring G1 to ring G8 are aromatic rings,
The corresponding R ^f is a group represented by the corresponding R ^g when the ring H1 to the ring H8 are an aromatic ring except for a 1-alkenyl group and an alkoxyl group.
Excludes a 1-alkenyl group and an alkoxyl group.

Ring G1 and ring H1 each independently represent a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group,
1,4-phenylene group optionally substituted by two fluorine atoms or methyl groups, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1-2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted with 1,4-cyclohexenylene group optionally substituted with 1 to 2 fluorine atoms, 1,3-dioxane-trans-
Represents a 2,5-diyl group, a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, and in each compound, transdecahydronaphthalene-trans-2,
6-diyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or two fluorine atoms A 1,4-cyclohexenylene group optionally substituted by a fluorine atom, 1,3
-Dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is trans-1,2 4-cyclohexylene group or 1
A 1,4-phenylene group which may be substituted by 2 to 2 fluorine atoms or methyl groups. Ring G2 and ring H2 each independently represent a trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-
2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, naphthalene-2,6-optionally substituted by 1 or more fluorine atoms Diyl group, tetrahydronaphthalene which may be substituted by 1 to 2 fluorine atoms
A 2,6-diyl group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, Tetrahydronaphthalene which may be substituted by 1 to 2 fluorine atoms
The number of 2,6-diyl groups is preferably one or less, in which case the other ring may be substituted by a trans-1,4-cyclohexylene group or one or two fluorine atoms or methyl groups. 1,4-phenylene group.
Ring G3 and ring H3 are each independently a 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms or a methyl group, and a naphthalene-2 optionally substituted with 1 or more fluorine atoms. , 6-diyl group, 1
Represents a tetrahydronaphthalene-2,6-diyl group which may be substituted by two or more fluorine atoms, and a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms in each compound It is preferable that the number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by one or two fluorine atoms is one or less.

The more preferable form of (C2) can be represented by the following general formulas (C2a) to (C2m).

[0155]

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In the above formula, ring G1, ring G2, ring G3, ring H
1, ring H2 and ring H3 have the same meanings as described above, ring I1 has the same meaning as ring G1, ring I2 has the same meaning as ring G2, and ring I3 has the same meaning as ring G3. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, 1-2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted with a 1,4-cyclohexenylene group optionally substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, Pyrimidine-2,
It is preferable that the number of 5-diyl group or pyridine-2,5-diyl group is one or less, and in that case, the other ring is trans-1,4-cyclohexylene group or 1-2 fluorine atoms or methyl group. Is a 1,4-phenylene group which may be substituted by

Next, a more preferred embodiment of (C3) can be represented by the following general formulas (C3a) to (C3f).

[0158]

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In the above formula, ring G1, ring G2, ring H1, ring H
2, Ring I1 and Ring I2 have the same meanings as described above, and Ring J1 has the same meaning as Ring G1 and Ring J2 has the same meaning as Ring G2. Further, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene which may be substituted with one or more fluorine atoms,
2,6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-optionally substituted by fluorine atom
The number of cyclohexenylene groups, 1,3-dioxane-trans-2,5-diyl groups, pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably one or less. The other ring is trans-1,4-
A cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or a methyl group.

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

(I-1) shown in Table 1

[0162]

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The compound (H) is a host liquid crystal (H) which is suitable as a low viscosity host liquid crystal having a wide temperature range and particularly suitable for active matrix driving.

[0164]

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A nematic liquid crystal composition (M-1) was prepared by adding 20% to the above, and the liquid crystal phase maximum temperature (T _NI ) was 84.1 ° C. This (M-1) is 1
After being left at 50 ° C. for 20 hours, its T _NI was measured. Although the ultraviolet irradiation for 20 hours, changes in T _NI was observed. Next, when the voltage holding ratio of this composition was measured, it showed a sufficiently high value at the time of preparation, after heating and after irradiation with ultraviolet rays, similarly to the host liquid crystal (H).

Next, (M-1) was converted to a T cell having a cell thickness of 4.5 μm.
A liquid crystal element was prepared by filling in an N cell, and its electro-optical characteristics were measured. The results were as follows.

Nematic phase upper limit temperature (T _NI ) 84.1 ° C. Dielectric anisotropy (Δε) 6.2 Threshold voltage (Vth) 1.49 V Response time (τ) 29.3 ms

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 ) 116.7 ° C. Dielectric anisotropy (Δε) 4.80 Threshold voltage (Vth) 1.88 V Response time (τ) 21.5 ms Here, the response time rises This is a response time at the time of voltage application in which the time (τr) and the fall time (τd) are equal. (M-1) has a large increase in dielectric anisotropy because four fluorine atoms, which are polar groups, are contained in the molecule. Therefore, the threshold voltage is reduced by 20% or more as compared with (H). . Normally, when the number of fluorine molecules in a molecule increases, T _NI
Is known to decrease, but the T _NI of (M-1) maintains a relatively high value of 84.1 ° C.

As described above, the compound of the general formula (I)
B) Low-voltage driving is possible to reduce the threshold voltage,
B) The decrease of T _NI is smaller than that of other fluorine-based liquid crystals,
(C) It can be seen that the method is very useful in preparing a liquid crystal composition capable of high-speed response and d) having a high voltage holding ratio and sufficient active matrix driving.

[0171]

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

Note that 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, an infrared resonance spectrum (IR), a mass spectrum (MS), and the like.

Example 1 Synthesis of 6- (4-propylphenyl) -1,2-difluoronaphthalene 6.2 g of 6-methoxynaphthalen-2-yl-boric acid
(This compound was obtained by reacting a Grignard reagent prepared from 5.0 g of 6-methoxy-2-bromonaphthalene with trimethyl borate followed by hydrolysis with hydrochloric acid) and 6.5 g of 4-propyliodobenzene. 2
1 mL of toluene, 10 mL of ethanol and 21 m
L of water, 5.9 g of potassium carbonate and 0.3 mg of tetrakistriphenylphosphine palladium (0) were added, and the mixture was stirred at 75 ° C. for 7 hours. Water and toluene were added, and dilute hydrochloric acid was further added until the aqueous layer became weakly acidic. The mixture was extracted with toluene, and the organic layers were combined, washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the mixture was refluxed with 40 mL of acetic acid and 40 mL of 40% hydrobromic acid for 10 hours to obtain 5.5 g of 6- (4-propylphenyl) naphthalen-6-ol. This 6
The total amount of-(4-propylphenyl) naphthalen-2-ol was dissolved in 20 mL of acetonitrile, and 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2,
2,2] octane bis (trifluoroborate) 1
5.0 g was added, and the mixture was stirred at room temperature for 18 hours. Water was added to stop the reaction, and the solvent was distilled off under reduced pressure. Toluene was added, washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained oil was purified by silica gel column chromatography (hexane / hexane).
Purified with ethyl acetate = 9/1). 20 mL of the obtained total amount and 7.8 g of bis- (2-methoxyethyl) aminosulfur trifluoride were added to tetrahydrofuran (THF).
And stirred at 80 ° C. for 8 hours. Water and toluene were added, and dilute hydrochloric acid was further added until the aqueous layer became weakly acidic. The mixture was extracted with toluene, and the organic layers were combined, washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was dissolved in 20 mL of ethyl acetate,
200 mg of 5% palladium carbon and 1 mL of triethylamine were added, and the mixture was stirred at a hydrogen pressure of 4 atm for 5 hours. After removing the catalyst by filtration through Celite, the solvent was distilled off, and diluted hydrochloric acid was further added until the aqueous layer became weakly acidic. The mixture was extracted with toluene, and the organic layers were combined, washed with water and then with a saturated saline solution, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane) and then recrystallized twice from ethanol to obtain 2.1 g of 6- (4-propylphenyl) -1,2-difluoronaphthalene as white crystals. Was.

Hereinafter, the following compounds are obtained in the same manner.

6- (4-methylphenyl) -1,2-difluoronaphthalene 6- (4-ethylphenyl) -1,2-difluoronaphthalene 6- (4-butylphenyl) -1,2-difluoronaphthalene 6 (4-pentylphenyl) -1,2-difluoronaphthalene 6- (4-hexylphenyl) -1,2-difluoronaphthalene 6- (4-heptylphenyl) -1,2-difluoronaphthalene

6- (4-methyl-2-fluorophenyl) -1,2-difluoronaphthalene 6- (4-ethyl-2-fluorophenyl) -1,2-
Difluoronaphthalene 6- (4-propyl-2-fluorophenyl) -1,2
-Difluoronaphthalene 6- (4-butyl-2-fluorophenyl) -1,2-
Difluoronaphthalene 6- (4-pentyl-2-fluorophenyl) -1,2
-Difluoronaphthalene 6- (4-hexyl-2-fluorophenyl) -1,2
-Difluoronaphthalene 6- (4-heptyl-2-fluorophenyl) -1,2
-Difluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) -1,2-difluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene 6- (4-propyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene 6- (4-butyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl)-
1,2-difluoronaphthalene

6- [4- (4-methylphenyl) phenyl] -1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] -1,2
-Difluoronaphthalene 6- [4- (4-propylphenyl) phenyl] -1,
2-difluoronaphthalene 6- [4- (4-butylphenyl) phenyl] -1,2
-Difluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] -1,
2-difluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] -1,
2-difluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] -1,
2-difluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propylphenyl) -2-fluorophenyl ] -1,2-Difluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-pentylphenyl) -2-fluorophenyl]- 1,2-difluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-heptylphenyl) -2-fluorophenyl] -1, 2-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] -1,2-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] -1,2-difluoronaphthalene

6- [4- (4-Methyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4 -Butyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2 -Difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4 (4-heptyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoro-naphthalene

6- [4- (4-methylphenyl) ethynylphenyl] -1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) ethynylphenyl]
-1,2-Difluoronaphthalene 6- [4- (4-propylphenyl) ethynylphenyl] -1,2-difluoronaphthalene 6- [4- (4-butylphenyl) ethynylphenyl]
-1,2-Difluoronaphthalene 6- [4- (4-pentylphenyl) ethynylphenyl] -1,2-difluoronaphthalene 6- [4- (4-hexylphenyl) ethynylphenyl] -1,2-difluoronaphthalene 6 -[4- (4-heptylphenyl) ethynylphenyl] -1,2-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2-
Difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) ethynyl-2- Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-pentyl-2 -Fluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [ 4- (4-heptyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2-difur Russia naphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl]-
1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluoro Phenyl) ethynyl-2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2-difluoronaphthalene 6 -[4- (4-pentyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2,6 -Difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ethynyl- , 6-difluorophenyl] -1,2-difluoro-naphthalene

6- [4- (4-methyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl]-
1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-propyl-2,6 -Difluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6 -[4- (4-pentyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) ethynyl-2 -Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) ethyl -2-fluorophenyl] -1,2-difluoro-naphthalene

Example 2 Synthesis of 6- (4-propylphenyl) -2,3-difluoronaphthalene In Example 1, 7-methoxynaphthalene- was used instead of 6-methoxynaphthalen-2-yl-boric acid. 6- (4-Propylphenyl) -2,3-difluoronaphthalene was obtained in the same manner except that 2-yl-boric acid was used.

The following compounds are obtained in the same manner.

6- (4-methylphenyl) -2,3-difluoronaphthalene 6- (4-ethylphenyl) -2,3-difluoronaphthalene 6- (4-butylphenyl) -2,3-difluoronaphthalene 6 (4-pentylphenyl) -2,3-difluoronaphthalene 6- (4-hexylphenyl) -2,3-difluoronaphthalene 6- (4-heptylphenyl) -2,3-difluoronaphthalene

6- (4-methyl-2-fluorophenyl) -2,3-difluoronaphthalene 6- (4-ethyl-2-fluorophenyl) -2,3-
Difluoronaphthalene 6- (4-propyl-2-fluorophenyl) -2,3
-Difluoronaphthalene 6- (4-butyl-2-fluorophenyl) -2,3-
Difluoronaphthalene 6- (4-pentyl-2-fluorophenyl) -2,3
-Difluoronaphthalene 6- (4-hexyl-2-fluorophenyl) -2,3
-Difluoronaphthalene 6- (4-heptyl-2-fluorophenyl) -2,3
-Difluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) -2,3-difluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene 6- (4-propyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene 6- (4-butyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl)-
2,3-difluoronaphthalene

6- [4- (4-methylphenyl) phenyl] -2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] -2,3
-Difluoronaphthalene 6- [4- (4-propylphenyl) phenyl] -2,
3-difluoronaphthalene 6- [4- (4-butylphenyl) phenyl] -2,3
-Difluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] -2,
3-difluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] -2,
3-difluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] -2,
3-difluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propylphenyl) -2-fluorophenyl ] -2,3-Difluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) -2-fluorophenyl]- 2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-heptylphenyl) -2-fluorophenyl] -2, 3-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] -2,3-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) -2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] -2,3-difluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4 -Butyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3 -Difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoronaphthalene 6- [4 (4-heptyl-2,6-difluorophenyl) -2-fluorophenyl] -2,3-difluoro-naphthalene

6- [4- (4-methylphenyl) ethynylphenyl] -2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) ethynylphenyl]
-2,3-difluoronaphthalene 6- [4- (4-propylphenyl) ethynylphenyl] -2,3-difluoronaphthalene 6- [4- (4-butylphenyl) ethynylphenyl]
-2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) ethynylphenyl] -2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) ethynylphenyl] -2,3-difluoronaphthalene 6 -[4- (4-heptylphenyl) ethynylphenyl] -2,3-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -2,3-
Difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) ethynyl-2- Fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2 -Fluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [ 4- (4-heptyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -2,3-difur Russia naphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl]-
2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluoro Phenyl) ethynyl-2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -2,3-difluoronaphthalene 6 -[4- (4-pentyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2,6 -Difluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ethynyl- , 6-difluorophenyl] -2,3-difluoro-naphthalene

6- [4- (4-methyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl]-
2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-propyl-2,6 -Difluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6 -[4- (4-pentyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) ethynyl-2 -Fluorophenyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) ethyl -2-fluorophenyl] -2,3-difluoro-naphthalene

Example 3 Synthesis of 6- (4-propylphenyl) -1,2,3-trifluoronaphthalene A solution of 30 g of 3,4,5-trifluorophenylacetic acid and 40.6 g of thionyl chloride in 60 mL of dichloroethane was used. Was added with a catalytic amount of pyridine, and the mixture was heated and refluxed for 5 hours under a nitrogen atmosphere. After distilling off dichloroethane, the residue was dissolved in 200 mL of dichloromethane, and the solution was dissolved in aluminum chloride 4 under ice-cooling.
It was added dropwise to a suspension of 0.5 g of dichloromethane in 80 mL. After stirring for 30 minutes, ethylene gas was blown in, and the mixture was further stirred for 5 hours. After dilute hydrochloric acid was added and the organic layer was separated, the aqueous layer was extracted with toluene. The organic layers were combined, washed successively with water, saturated aqueous sodium hydrogen carbonate, water and saturated saline, dried over anhydrous sodium sulfate and dried, and the solvent was distilled off.
2mmHg) to give 1,2,3-trifluoro-5,7,8-trihydronaphthalen-6-one 1
6.1 g were obtained.

Next, 2.9 g of magnesium was added to 3 mL of THF.
And a solution of 21.3 g of 4-propylbromobenzene in 80 mL of THF was added dropwise over about 30 minutes at a speed at which THF was gently refluxed. After stirring for an additional hour,
A solution of 16.1 g of 2,3-trifluoro-5,7,8-trihydronaphthalen-6-one in 60 mL of THF was added to 30 mL of THF.
It was dropped over a period of minutes. After further stirring for 1 hour, 10% hydrochloric acid 5
0 mL was added. 100 mL of hexane was added, the organic layer was separated, the aqueous layer was extracted with 100 mL of hexane, and the organic layers were combined. The extract was washed with water, saturated aqueous sodium hydrogen carbonate, and saturated saline, and dried over anhydrous sodium sulfate. The solvent is distilled off and toluene 100
mL and 1.7 g of p-toluenesulfonic acid monohydrate were added, and the mixture was heated and stirred at 110 ° C. while distilling off water. After the water distills out, return to room temperature and add water 5
0 mL was added and the organic layer was separated. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution, and dried over anhydrous sodium sulfate. This product is dissolved in 60 g of dichloromethane,
A solution of 18.8 g of bromine in 60 g of dichloromethane was added dropwise. After stirring for an additional hour, water was added to stop the reaction, the organic layer was separated, washed with water, saturated aqueous sodium bicarbonate and saturated saline, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane), and further recrystallized from ethanol to give 6- (4-propylphenyl) -1,2,3-trifluoronaphthalene.
1.6 g were obtained.

The following compounds are obtained in the same manner.

6- (4-methylphenyl) -1,2,3
-Trifluoronaphthalene 6- (4-ethylphenyl) -1,2,3-trifluoronaphthalene 6- (4-butylphenyl) -1,2,3-trifluoronaphthalene 6- (4-pentylphenyl) -1 , 2,3-Trifluoronaphthalene 6- (4-hexylphenyl) -1,2,3-trifluoronaphthalene 6- (4-heptylphenyl) -1,2,3-trifluoronaphthalene

6- (4-Methyl-2-fluorophenyl) -1,2,3-trifluoronaphthalene 6- (4-ethyl-2-fluorophenyl) -1,2,2
3-trifluoronaphthalene 6- (4-propyl-2-fluorophenyl) -1,
2,3-trifluoronaphthalene 6- (4-butyl-2-fluorophenyl) -1,2,2
3-trifluoronaphthalene 6- (4-pentyl-2-fluorophenyl) -1,
2,3-trifluoronaphthalene 6- (4-hexyl-2-fluorophenyl) -1,
2,3-trifluoronaphthalene 6- (4-heptyl-2-fluorophenyl) -1,
2,3-trifluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) -1,2,3-trifluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene 6- (4-propyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene 6- (4-butyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl)-
1,2,3-trifluoronaphthalene

6- [4- (4-methylphenyl) phenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4-propylphenyl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] -1,
2,3-trifluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propylphenyl) ) -2-Fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- ( 4-pentylphenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6 [4- (4-heptylphenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)- 2
-Fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2,6 -Difluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3- Trifluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2,6- Difluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) -2-fluorophene Le] -1,2,3-trifluoro-naphthalene

6- [4- (4-methylphenyl) ethynylphenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) ethynylphenyl]
-1,2,3-trifluoronaphthalene 6- [4- (4-propylphenyl) ethynylphenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) ethynylphenyl]
-1,2,3-trifluoronaphthalene 6- [4- (4-pentylphenyl) ethynylphenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) ethynylphenyl] -1 , 2,3-trifluoronaphthalene 6- [4- (4-heptylphenyl) ethynylphenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,2
3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluoro Phenyl) ethynyl-2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-trifluoro Naphthalene 6- [4- (4-pentyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl- 2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ethynyl-2 Fluorophenyl] -1,2,3-trifluoro-naphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl]-
1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4 -Propyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluoro Phenyl) ethynyl-2,6-difluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3-
Trifluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl]-
1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3-
Trifluoronaphthalene

Example 4 Synthesis of 6- (4-propylphenyl) -1,2,3,8-tetrafluoronaphthalene 1,2,3,8-tetrafluoronaphthalen-2-yl-borate 39. 9 g (this compound was obtained by reacting a Grignard reagent prepared from 50 g of 1,2,3,8-tetrafluoro-2-bromonaphthalene with trimethyl borate and then hydrolyzing with hydrochloric acid) and 4-propyl Is dissolved in 190 mL of toluene, 90 mL of ethanol and 190 mL of water, and 40.5 g of potassium carbonate and 2.0 mg of tetrakistriphenylphosphine palladium (0) are added thereto.
For 12 hours. Water and toluene were added, and dilute hydrochloric acid was further added until the aqueous layer became weakly acidic. Extracted with toluene, combined the organic layers, washed with water and then with saturated saline,
It was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained oil was purified by silica gel column chromatography (hexane), and then recrystallized twice from ethanol to give 6- (4-propylphenyl) -1,1.
2,3,8-tetrafluoronaphthalene white crystal 2
6.7 g were obtained.

Hereinafter, the following compounds are obtained in the same manner.

6- (4-methylphenyl) -1,2,2
3,8-tetrafluoronaphthalene 6- (4-ethylphenyl) -1,2,3,8-tetrafluoronaphthalene 6- (4-butylphenyl) -1,2,3,8-tetrafluoronaphthalene 6- ( 4-pentylphenyl) -1,2,3,8-tetrafluoronaphthalene 6- (4-hexylphenyl) -1,2,3,8-tetrafluoronaphthalene 6- (4-heptylphenyl) -1,2,2 3,8-tetrafluoronaphthalene

6- (4-methyl-2-fluorophenyl) -1,2,3,8-tetrafluoronaphthalene 6- (4-ethyl-2-fluorophenyl) -1,2,2
3,8-tetrafluoronaphthalene 6- (4-propyl-2-fluorophenyl) -1,
2,3,8-tetrafluoronaphthalene 6- (4-butyl-2-fluorophenyl) -1,2,2
3,8-tetrafluoronaphthalene 6- (4-pentyl-2-fluorophenyl) -1,
2,3,8-tetrafluoronaphthalene 6- (4-hexyl-2-fluorophenyl) -1,
2,3,8-tetrafluoronaphthalene 6- (4-heptyl-2-fluorophenyl) -1,
2,3,8-tetrafluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) -1,2,3,8-tetrafluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene 6- (4-propyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene 6- (4-butyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl)-
1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methylphenyl) phenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene 6- [4- (4-propylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] -1,
2,3,8-tetrafluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- ( 4-propylphenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] -1,2,3,8-tetra Fluoronaphthalene 6- [4- (4-pentylphenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] -1 , 2,3,8-Tetrafluoronaphthalene 6- [4- (4-heptylphenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2-fluorophenyl] -1,2,3,8-
Tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] -1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] -1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4- Propyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [ 4- (4-hexyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2,6- Fluorophenyl) -2-fluorophenyl] -1,2,3,8- tetrafluoro naphthalene

6- [4- (4-methylphenyl) ethynylphenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) ethynylphenyl]
-1,2,3,8-Tetrafluoronaphthalene 6- [4- (4-propylphenyl) ethynylphenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) ethynyl Phenyl]
-1,2,3,8-Tetrafluoronaphthalene 6- [4- (4-pentylphenyl) ethynylphenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) ethynyl Phenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) ethynylphenyl] -1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl -2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1, 2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4 -Hexyl-2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl 2-fluorophenyl) ethynyl-2-fluorophenyl] -1,2,3,8- tetrafluoro naphthalene

6- [4- (4-methyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl]-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3,8
-Tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3,
8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3,8
-Tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ethynyl-2,6-difluorophenyl] -1,2,3
8-tetrafluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl]-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) ethynyl-2-fluorophenyl] -1,2,3
8-tetrafluoronaphthalene

6- (4-vinylphenyl) -1,2-difluoronaphthalene 6- [4- (3-buten-1-yl) phenyl] -1,
2-difluoronaphthalene 6- [4- (2-buten-1-yl) phenyl] -1,
2-difluoronaphthalene

6- (4-vinylphenyl) -1,2,3
-Trifluoronaphthalene 6- [4- (3-buten-1-yl) phenyl] -1,
2,3-trifluoronaphthalene 6- [4- (2-buten-1-yl) phenyl] -1,
2,3-trifluoronaphthalene

6- (4-vinyl-2-fluorophenyl) -1,2-difluoronaphthalene 6- [4- (3-buten-1-yl) -2-fluorophenyl] -1,2-difluoronaphthalene 6 -[4- (2-buten-1-yl) -2-fluorophenyl] -1,2-difluoronaphthalene

6- (4-vinyl-2-fluorophenyl) -1,2,3-trifluoronaphthalene 6- [4- (3-buten-1-yl) -2-fluorophenyl] -1,2,2 3-trifluoronaphthalene 6- [4- (2-buten-1-yl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene

6- (4-vinyl-2,6-difluorophenyl) -1,2-difluoronaphthalene 6- [4- (3-buten-1-yl) -2,6-difluorophenyl] -1,2 -Difluoronaphthalene 6- [4- (2-buten-1-yl) -2,6-difluorophenyl] -1,2-difluoronaphthalene

6- (4-vinyl-2,6-difluorophenyl) -1,2,3-trifluoronaphthalene 6- [4- (3-buten-1-yl) -2,6-difluorophenyl]- 1,2,3-trifluoronaphthalene 6- [4- (2-buten-1-yl) -2,6-difluorophenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-vinylphenyl) phenyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) phenyl)
Phenyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
Phenyl] -1,2-difluoronaphthalene

6- [4- (4-Vinylphenyl) phenyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) phenyl)
Phenyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
Phenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-vinylphenyl) -2-
Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) phenyl)
-2-Fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
-2-fluorophenyl] -1,2-difluoronaphthalene

6- [4- (4-vinylphenyl) -2-
Fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) phenyl)
-2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
-2-fluorophenyl] -1,2,3-trifluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2 -Fluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2-fluorophenyl) -2-fluorophenyl] -1,2 -Difluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) -2-fluorophenyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) ) -2-Fluorophenyl) -2-fluorophenyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2-fluorophenyl) -2-fluorophenyl] -1,2,3
-Trifluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) −2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2-difluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2-fluorophenyl) -2,6-difluorophenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2,3-trifluoronaphthalene

6- [4- (4-vinyl-2,6-difluorophenyl) -2-fluorophenyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) −2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2-difluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) -2,6-difluorophenyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) -2-fluorophenyl] -1,
2,3-trifluoronaphthalene

Example 5 Synthesis of 6- [4- (4-propylphenyl) cyclohexyl] -1,2-difluoronaphthalene 5.6 g of magnesium was suspended in 10 mL of THF.
-Methoxybromonaphthalene 50 g THF 200 mL
The solution was added dropwise over about 1 hour at a rate at which the THF refluxed gently. After further stirring for 1 hour, 55.0 g of 4- (4-propylphenyl) cyclohexanone in 220 mL of THF
The solution was added dropwise over 1 hour. After stirring for an additional hour, 10
100% hydrochloric acid was added. 100 mL of hexane was added, the organic layer was separated, the aqueous layer was extracted with 100 mL of hexane, and the organic layers were combined. The extract was washed with water, saturated aqueous sodium hydrogen carbonate, and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off, and 100 mL of toluene and 4.7 g of p-toluenesulfonic acid monohydrate were added.
The mixture was heated and stirred at 0 ° C. After the evaporation of water had ceased, the temperature was returned to room temperature, 50 mL of water was added, and the organic layer was separated. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the whole amount was adjusted to ethyl acetate 20.
0%, 5% palladium / carbon (water-containing) 8.0
g was added and the mixture was stirred in an autoclave under a hydrogen pressure of 4 kg / cm ² . After stirring at room temperature for 5 hours, the catalyst was removed by filtration through Celite, and the solvent was distilled off. The resulting crude product was refluxed with 200 mL of acetic acid and 200 mL of hydrobromic acid. 200 mL of toluene was added, and the organic layer was separated. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution, and dried over anhydrous sodium sulfate. After evaporating the solvent, the cyclohexane ring is isomerized to trans with a strong base (potassium-t-butoxide) in DMF and recrystallized to give 6- [4- (4-
Propylphenyl) cyclohexyl] naphthalene-2-
48.5 g of all white crystals were obtained. The obtained 6- [4
By fluorinating-(4-propylphenyl) cyclohexyl] naphthalen-2-ol in the same manner as in Example 1, 21.2 g of 6- [4- (4-propylphenyl) cyclohexyl] -1,2-difluoronaphthalene was obtained. Obtained.

The following compounds are obtained in the same manner.

6- [4- (4-methylphenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl]-
1,2-difluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl]-
1,2-difluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
-1,2-Difluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
-1,2-Difluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
-1,2-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] -1,2-difluoro Naphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6 -[4- (4-Pentyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [ 4- (4-heptyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthale

6- [4- (4-Methyl-2,6-difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] -1 , 2-Difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) cyclohexyl] -1,2-Difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) Cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) cy Rohekishiru] -1,2-difluoro-naphthalene

6- [4- (4-Methylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-propylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-butylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-pentylphenylethynyl) cyclohexyl ] -1,2-Difluoronaphthalene 6- [4- (4-hexylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-heptylphenylethynyl) cyclohexyl] -1,2-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenylethynyl) cyclohexyl] -1,2 -Difluoronaphthalene 6- [4- (4-propyl-2-fluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenylethynyl) cyclohexyl] -1,2 -Difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenylethynyl) cyclohexyl] -1,2 -Difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) Ethynyl) cyclohexyl] -1,2-difluoro-naphthalene

6- [4- (4-Methyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2-Difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl Ethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4-hexyl-2, 6-difluorophenylethynyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4 (4-heptyl-2,6-difluorophenyl ethynyl) cyclohexyl] -1,2-difluoro-naphthalene

Example 6 Synthesis of 6- [4- (4-propylphenyl) cyclohexyl] -2,3-difluoronaphthalene 5.5 g of magnesium was suspended in 10 mL of THF.
THF2 of 50 g of 2,3-difluorobromonaphthalene
The 00 mL solution was added dropwise over about 1 hour at a rate at which the THF was gently refluxed. After stirring for another 1 hour, 53.7 g of 4- (4-propylphenyl) cyclohexanone in THF2
The 20 mL solution was added dropwise over 1 hour. After further stirring for 1 hour, 100 mL of 10% hydrochloric acid was added. Hexane 100m
L, the organic layer was separated, and the aqueous layer was 100 mL of hexane.
And the organic layers were combined. The extract was washed with water, saturated aqueous sodium hydrogen carbonate, and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off, 100 mL of toluene and 4.6 g of p-toluenesulfonic acid monohydrate were added, and the mixture was heated and stirred at 110 ° C. while separating and removing the distilled water. After the water distills out,
After returning to room temperature, 50 mL of water was added, and the organic layer was separated. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent was distilled off, the whole amount was dissolved in 200 mL of ethyl acetate, and 5% palladium / carbon (water-containing) was added.
8.0 g, and in an autoclave, hydrogen pressure 4 kg / c
Stirred under m ² . After stirring at room temperature for 5 hours, the catalyst was removed by filtration through Celite, the solvent was distilled off, and the cyclohexane ring was isomerized to trans with potassium-t-butoxide in DMF, purified by silica gel column chromatography (hexane), and then ethanol. Recrystallized twice from to give white crystals of 6- [4- (4-propylphenyl) cyclohexyl] -2,3-difluoronaphthalene.
3 g were obtained.

Hereinafter, the following compounds are obtained in the same manner.

6- [4- (4-methylphenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl]-
2,3-difluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl]-
2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
-2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
-2,3-difluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
-2,3-difluoronaphthalene

6- [4- (4-methylphenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl]-
1,2,3-trifluoronaphthalene 6- [4- (4-propylphenyl) cyclohexyl]
-1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl]-
1,2,3-trifluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
-1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
-1,2,3-trifluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
-1,2,3-trifluoronaphthalene

6- [4- (4-methylphenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl]-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propylphenyl) cyclohexyl]
-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl]-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
-1,2,3,8-tetrafluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] -2,3-difluoro Naphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6 -[4- (4-hexyl-2-fluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) cyclohexyl] -2,3-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] -1, 2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl ] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2- Fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) cyclohexyl Sill] -1,2,3-trifluoro-naphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl]- 1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl- 2-fluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hep -2-fluorophenyl) cyclohexyl] -1,2,3,8- tetra-fluoro-naphthalene

6- [4- (4-Methyl-2,6-difluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] -2 , 3-Difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) Cyclohexyl] -2,3-difluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl ] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl- 2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hep Le-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoro-naphthalene

6- [4- (4-methyl-2,6-difluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) ) Cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4 -(4-butyl-2,6-difluorophenyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] -1,2 , 3,8-Tetrafluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) cyclohexyl] -1,2,3,8-tetraf Oro naphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) cyclohexyl] -1,2,3,8- tetra-fluoro-naphthalene

6- [4- (4-Methylphenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-ethylphenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-butylphenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-pentylphenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-hexylphenylethynyl) cyclohexyl ] -2,3-Difluoronaphthalene 6- [4- (4-heptylphenylethynyl) cyclohexyl] -2,3-difluoronaphthalene

6- [4- (4-Methylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenylethynyl) cyclohexyl] -1,2,3-trifluoro Naphthalene 6- [4- (4-propylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6 -[4- (4-Pentylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [ 4- (4-heptylphenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthale

6- [4- (4-methylphenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenylethynyl) cyclohexyl] -1,2,3,3 8-tetrafluoronaphthalene 6- [4- (4-propylphenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenylethynyl) cyclohexyl] -1,2, 3,8-tetrafluoronaphthalene 6- [4- (4-pentylphenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenylethynyl) cyclohexyl] -1, 2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenylethynyl) cyclohexyl -1,2,3,8- tetrafluoro naphthalene

6- [4- (4-Methyl-2-fluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-Ethyl-2-fluorophenylethynyl) cyclohexyl] -2,3 -Difluoronaphthalene 6- [4- (4-butyl-2-fluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenylethynyl) cyclohexyl] -2,3 -Difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenylethynyl) cyclohexyl] -2,3 -Difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenylethynyl) cyclohexyl]- 1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluoro Phenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4 -Hexyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4 (4-heptyl-2-fluoro-phenylethynyl) cyclohexyl] -1,2,3-trifluoro-naphthalene

6- [4- (4-Methyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3,8-
Tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenylethynyl) cyclohexyl ] -1,2,3,8-Tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4 -Pentyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenylethynyl) cyclohexyl] -1,2,3,8- Tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenylethynyl) cyclohexyl] 1,2,3,8- tetrafluoro naphthalene

6- [4- (4-Methyl-2,6-difluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl Ethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene 6- [4- (4-heptyl-2, 6-difluorophenylethynyl) cyclohexyl] -2,3-difluoronaphthalene

6- [4- (4-Methyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3
-Trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) Ethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- ( 4-pentyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3 -Trifluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenylethynyl) cyclohexyl Le] -1,2,3-trifluoro-naphthalene

6- [4- (4-methyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2 , 6-Difluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3,8- Tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2,6-difluoro Phenylethynyl) cyclohexyl] -1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2,6- Fluorophenylethynyl) cyclohexyl] -1,2,3,8- tetra-fluoro-naphthalene

Example 7 Synthesis of 6- (4-propylphenyl) ethynyl-2,3-difluoronaphthalene In Example 6, 4-propyl-1-ethynyl was used in place of 4- (4-propylphenyl) cyclohexanone. 6- (4) in the same manner except that isomerization was not performed using benzene.
-Propylphenyl) ethynyl-2,3-difluoronaphthalene was obtained.

Hereinafter, the following compounds are obtained in the same manner.

6- (4-methylphenyl) ethynyl-
2,3-difluoronaphthalene 6- (4-ethylphenyl) ethynyl-2,3-difluoronaphthalene 6- (4-butylphenyl) ethynyl-2,3-difluoronaphthalene 6- (4-pentylphenyl) ethynyl-2, 3-difluoronaphthalene 6- (4-hexylphenyl) ethynyl-2,3-difluoronaphthalene 6- (4-heptylphenyl) ethynyl-2,3-difluoronaphthalene

6- (4-methyl-2-fluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-ethyl-2-fluorophenyl) ethynyl-
2,3-difluoronaphthalene 6- (4-propyl-2-fluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-butyl-2-fluorophenyl) ethynyl-
2,3-difluoronaphthalene 6- (4-pentyl-2-fluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-hexyl-2-fluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4 -Heptyl-2-fluorophenyl) ethynyl-2,3-difluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- ( 4-propyl-2,6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-butyl-2,6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-pentyl-2, 6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl) ethynyl-2,3-difluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl) ethynyl -2,3-difluoronaphthalene

6- (4-methylphenyl) ethynyl-
1,2-difluoronaphthalene 6- (4-ethylphenyl) ethynyl-1,2-difluoronaphthalene 6- (4-propylphenyl) ethynyl-1,2-difluoronaphthalene 6- (4-butylphenyl) ethynyl-1, 2-difluoronaphthalene 6- (4-pentylphenyl) ethynyl-1,2-difluoronaphthalene 6- (4-hexylphenyl) ethynyl-1,2-difluoronaphthalene 6- (4-heptylphenyl) ethynyl-1,2- Difluoronaphthalene

6- (4-methyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-ethyl-2-fluorophenyl) ethynyl-
1,2-difluoronaphthalene 6- (4-propyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-butyl-2-fluorophenyl) ethynyl-
1,2-difluoronaphthalene 6- (4-pentyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-hexyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4 -Heptyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- ( 4-propyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-butyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-pentyl-2, 6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl) ethynyl -1,2-difluoronaphthalene

6- (4-methylphenyl) ethynyl-
1,2,3-trifluoronaphthalene 6- (4-ethylphenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-propylphenyl) ethynyl-1,2,3-
Trifluoronaphthalene 6- (4-butylphenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-pentylphenyl) ethynyl-1,2,3-
Trifluoronaphthalene 6- (4-hexylphenyl) ethynyl-1,2,3-
Trifluoronaphthalene 6- (4-heptylphenyl) ethynyl-1,2,3-
Trifluoronaphthalene

6- (4-methyl-2-fluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-ethyl-2-fluorophenyl) ethynyl-
1,2,3-trifluoronaphthalene 6- (4-propyl-2-fluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-butyl-2-fluorophenyl) ethynyl-
1,2,3-trifluoronaphthalene 6- (4-pentyl-2-fluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-hexyl-2-fluorophenyl) ethynyl-1,2, 3-trifluoronaphthalene 6- (4-heptyl-2-fluorophenyl) ethynyl-1,2,3-trifluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl) ethynyl-1,2,3- Trifluoronaphthalene 6- (4-propyl-2,6-difluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-butyl-2,6-difluorophenyl) ethynyl-1,2,3- Trifluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- (4-hexyl-2,6-difluorophenyl) ethynyl-1,2,3- Trifluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl) ethynyl-1,2,3-trifluoronaphthalene

6- (4-methylphenyl) ethynyl-
1,2,3,8-tetrafluoronaphthalene 6- (4-ethylphenyl) ethynyl-1,2,3,8
-Tetrafluoronaphthalene 6- (4-propylphenyl) ethynyl-1,2,3
8-tetrafluoronaphthalene 6- (4-butylphenyl) ethynyl-1,2,3,8
-Tetrafluoronaphthalene 6- (4-pentylphenyl) ethynyl-1,2,3,
8-tetrafluoronaphthalene 6- (4-hexylphenyl) ethynyl-1,2,3
8-tetrafluoronaphthalene 6- (4-heptylphenyl) ethynyl-1,2,3
8-tetrafluoronaphthalene

6- (4-methyl-2-fluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-ethyl-2-fluorophenyl) ethynyl-
1,2,3,8-tetrafluoronaphthalene 6- (4-propyl-2-fluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-butyl-2-fluorophenyl) ethynyl-
1,2,3,8-tetrafluoronaphthalene 6- (4-pentyl-2-fluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-hexyl-2-fluorophenyl) ethynyl- 1,2,3,8-tetrafluoronaphthalene 6- (4-heptyl-2-fluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene

6- (4-methyl-2,6-difluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-ethyl-2,6-difluorophenyl) ethynyl-1,2,2 3,8-tetrafluoronaphthalene 6- (4-propyl-2,6-difluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-butyl-2,6-difluorophenyl) ethynyl- 1,2,3,8-tetrafluoronaphthalene 6- (4-pentyl-2,6-difluorophenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-hexyl-2,6-difluoro Phenyl) ethynyl-1,2,3,8-tetrafluoronaphthalene 6- (4-heptyl-2,6-difluorophenyl) ethynyl-1,2,3 8 tetrafluoro naphthalene

6- [4- (4-Methylphenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propylphenyl) cyclohexyl]
Ethynyl-2,3-difluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
Ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
Ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
Ethynyl-2,3-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3 -Difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3 -Difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) cyclohexyl] ethynyl-2,3 -Difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ) Cyclohexyl] ethynyl-2,3-difluoro-naphthalene

6- [4- (4-Methyl-2,6-difluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] ethynyl -2,3-difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ) Cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexyl-2, 6-difluorophenyl) cyclohexyl] ethynyl-2,3-difluoronaphthalene 6- [4 (4-heptyl-2,6-difluorophenyl) cyclohexyl] ethynyl-2,3-difluoro-naphthalene

6- [4- (4-Methylphenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-propylphenyl) cyclohexyl]
Ethynyl-1,2-difluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
Ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
Ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
Ethynyl-1,2-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2 -Difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2 -Difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2 -Difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) ) Cyclohexyl] ethynyl-1,2-difluoro-naphthalene

6- [4- (4-Methyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] ethynyl -1,2-Difluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) ) Cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexyl-2, 6-difluorophenyl) cyclohexyl] ethynyl-1,2-difluoronaphthalene 6- [4 (4-heptyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2-difluoro-naphthalene

6- [4- (4-Methylphenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl] ethynyl-1,2,3-trifluoro Naphthalene 6- [4- (4-propylphenyl) cyclohexyl]
Ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-pentylphenyl) cyclohexyl]
Ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
Ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
Ethynyl-1,2,3-trifluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] ethynyl- 1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluoro Phenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4 -Hexyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4 (4-heptyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoro-naphthalene

6- [4- (4-methyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3
-Trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) ) Cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- ( 4-pentyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3 -Trifluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) cyclohexyl] e Sulfonyl-1,2,3-trifluoro-naphthalene

6- [4- (4-methylphenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) cyclohexyl] ethynyl-1,2,3 8-tetrafluoronaphthalene 6- [4- (4-propylphenyl) cyclohexyl]
Ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentylphenyl) Cyclohexyl]
Ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) cyclohexyl]
Ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) cyclohexyl]
Ethynyl-1,2,3,8-tetrafluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3,8-
Tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl) cyclohexyl] Ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4 -Pentyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl) cyclohexyl] ethynyl-1,2,3,8- Tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl) cyclohexyl] ethynyl 1,2,3,8- tetrafluoro naphthalene

6- [4- (4-methyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2 , 6-Difluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3,8- Tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2,6-difluoro Phenyl) cyclohexyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2,6- Fluorophenyl) cyclohexyl] ethynyl -1,2,3,8- tetrafluoro naphthalene

6- [4- (4-Methylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-Propylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] Ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] ethynyl-1,2-difluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-propylphenyl) -2- Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentylphenyl) -2- Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptylphenyl) -2- Fluorophenyl] ethynyl-1,2-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2-fluorophenyl] ethynyl-1,2-
Difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] ethynyl-1,2-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] ethynyl-
1,2-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2-difluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-
1,2-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-propyl-2,6 -Difluorophenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6 -[4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2- Fluorophenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) -2 Fluorophenyl] ethynyl-1,2-difluoro-naphthalene

6- [4- (4-methylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] Ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] ethynyl-2,3-difluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propylphenyl) -2- Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentylphenyl) -2- Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptylphenyl) -2- Fluorophenyl] ethynyl-2,3-difluoronaphthalene

6- [4- (4-Methyl-2-fluorophenyl) -2-fluorophenyl] ethynyl-2,3-
Difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] ethynyl-2,3-difluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] ethynyl-
2,3-difluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-difluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-2,3-difluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-
2,3-difluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-propyl-2,6 -Difluorophenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6 -[4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2- Fluorophenyl] ethynyl-2,3-difluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) -2 Fluorophenyl] ethynyl-2,3-difluoro-naphthalene

6- [4- (4-methylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] ethynyl-1,2,3-trifluoro Naphthalene 6- [4- (4-propylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene 6 -[4- (4-Pentylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [ 4- (4-heptylphenyl) phenyl] ethynyl-1,2,3-trifluoronaphthalene

6- [4- (4-methylphenyl) -2-
Fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4- Propylphenyl) -2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-Pentylphenyl) -2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-hexylphenyl) -2-fluorophenyl] ethynyl-1,2,3 -Trifluoronaphthalene 6- [4- (4-heptylphenyl) -2-fluorophenyl] ethynyl-1,2,3-trifluorona The array type

6- [4- (4-methyl-2-fluorophenyl) -2-fluorophenyl] ethynyl-1,2,2
3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-Fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] ethynyl-
1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-
1,2,3-trifluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3-
Trifluoronaphthalene

6- [4- (4-methylphenyl) phenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) phenyl] ethynyl-1,2,3 8-tetrafluoronaphthalene 6- [4- (4-propylphenyl) phenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) phenyl] ethynyl-1,2,2 3,8-tetrafluoronaphthalene 6- [4- (4-pentylphenyl) phenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) phenyl] ethynyl-1, 2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) phenyl] ethynyl-1,2,3,8-tetrafluoronaphthale

6- [4- (4-methylphenyl) -2-
Fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethylphenyl) -2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4 -(4-Propylphenyl) -2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butylphenyl) -2-fluorophenyl] ethynyl-1,2,3 , 8-Tetrafluoronaphthalene 6- [4- (4-pentylphenyl) -2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexylphenyl) -2- Fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptylphenyl) -2-fluorophenyl] Ethynyl -1,2,3,8- tetrafluoro naphthalene

6- [4- (4-methyl-2-fluorophenyl) -2-fluorophenyl] ethynyl-1,2,2
3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl) -2
-Fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2-fluorophenyl] ethynyl-1,2,3,8-tetrafluoronaphthalene

6- [4- (4-methyl-2-fluorophenyl) -2,6-difluorophenyl] ethynyl-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-propyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-butyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-pentyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-hexyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-heptyl-2-fluorophenyl)-
2,6-Difluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene

6- [4- (4-methyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-
1,2,3,8-tetrafluoronaphthalene 6- [4- (4-ethyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3,3
8-tetrafluoronaphthalene 6- [4- (4-propyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-butyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3
8-tetrafluoronaphthalene 6- [4- (4-pentyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3,
8-tetrafluoronaphthalene 6- [4- (4-hexyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3,
8-tetrafluoronaphthalene 6- [4- (4-heptyl-2,6-difluorophenyl) -2-fluorophenyl] ethynyl-1,2,3,
8-tetrafluoronaphthalene

Example 8 Synthesis of 6- [4- (4-vinylphenyl) cyclohexyl] -1,2-difluoronaphthalene In Example 6, 4- (4-propylphenyl) cyclohexanone was replaced by 4- ( 4-methoxymethylphenyl) except that cyclohexanone is used.
After obtaining [4- (4-methoxymethylphenyl) cyclohexyl] -2,3-difluoronaphthalene, the phenethyl alcohol protected by the methoxy group is deprotected and oxidized to an aldehyde, followed by odor. 6- [4- (4-vinylphenyl) by reacting a Wittig reagent prepared from methyltriphenylphosphonium bromide and potassium tert-butoxide
Cyclohexyl] -1,2-difluoronaphthalene can be produced.

Hereinafter, the following compounds are obtained in the same manner.

6- [4- (4- (3-Buten-1-yl) phenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
Cyclohexyl] -1,2-difluoronaphthalene

6- [4- (4-Vinylphenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) phenyl)
Cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) phenyl)
Cyclohexyl] -1,2,3-trifluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2-fluorophenyl) Cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2-fluorophenyl) cyclohexyl] -1,2-difluoronaphthalene

6- [4- (4-vinyl-2-fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2- Fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2-fluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene

6- [4- (4-vinyl-2,6-difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4- (3-buten-1-yl) -2,6 −
Difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) cyclohexyl] -1,2-difluoronaphthalene

6- [4- (4-vinyl-2,6-difluorophenyl) cyclohexyl] -1,2,3-trifluoronaphthalene 6- [4- (4- (3-buten-1-yl)- 2,6-
Difluorophenyl) cyclohexyl] -1,2,3-
Trifluoronaphthalene 6- [4- (4- (2-buten-1-yl) -2,6-
Difluorophenyl) cyclohexyl] -1,2,3-
Trifluoronaphthalene

Example 9 Synthesis of 6- (4-vinylphenyl) ethynyl-1,2-difluoronaphthalene In Example 7, 4-methoxymethyl-1-ethynylbenzene was used in place of 4-propyl-1-ethynylbenzene. 6- (4-methoxymethylphenyl) ethynyl-2,3-difluoronaphthalene was obtained in the same manner except that was used, demethylated, and then oxidized to aldehyde, which was added to methyltriphenylphosphonium bromide. And a 6- (4-vinylphenyl) by reacting a Wittig reagent prepared from and potassium-t-butoxide.
Ethynyl-1,2-difluoronaphthalene was obtained.

Hereinafter, the following compounds are obtained in the same manner.

6- [4- (3-Buten-1-yl) phenyl] ethynyl-1,2-difluoronaphthalene 6- [4- (2-buten-1-yl) phenyl] ethynyl-1,2-difluoro Naphthalene

6- (4-vinylphenyl) ethynyl-
1,2,3-trifluoronaphthalene 6- [4- (3-
(Buten-1-yl) phenyl] ethynyl-1,2,3-
Trifluoronaphthalene 6- [4- (2-buten-1-yl) phenyl] ethynyl-1,2,3-trifluoronaphthalene

6- (4-vinyl-2-fluorophenyl) ethynyl-1,2-difluoronaphthalene 6- [4- (3-buten-1-yl) -2-fluorophenyl] ethynyl-1,2-difluoro Naphthalene 6- [4- (2-buten-1-yl) -2-fluorophenyl] ethynyl-1,2-difluoronaphthalene

6- (4-vinyl-2-fluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- [4- (3-buten-1-yl) -2-fluorophenyl] ethynyl-1, 2,3-trifluoronaphthalene 6- [4- (2-buten-1-yl) -2-fluorophenyl] ethynyl-1,2,3-trifluoronaphthalene

6- (4-vinyl-2,6-difluorophenyl) ethynyl-1,2-difluoronaphthalene 6- [4- (3-buten-1-yl) -2,6-difluorophenyl] ethynyl-1 , 2-Difluoronaphthalene 6- [4- (2-buten-1-yl) -2,6-difluorophenyl] ethynyl-1,2-difluoronaphthalene

6- (4-vinyl-2-fluoro-2,6
-Difluorophenyl) ethynyl-1,2,3-trifluoronaphthalene 6- [4- (3-buten-1-yl) -2,6-difluorophenyl] ethynyl-1,2,3-trifluoronaphthalene 6- [4- (2-buten-1-yl) -2,6-difluorophenyl] ethynyl-1,2,3-trifluoronaphthalene

(Example 10) Preparation of liquid crystal composition (1) Host liquid crystal (H) suitable as a nematic liquid crystal having a low viscosity and a wide temperature range, particularly suitable for active matrix driving

[0337]

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(Cyclohexane ring is in trans configuration) showed a nematic phase at 116.7 ° C. or lower. This (H) was filled in a TN cell having a cell thickness of 4.5 μm to prepare a liquid crystal element, and the physical properties and electro-optical properties of the liquid crystal element were as follows.

Nematic phase maximum temperature (T _NI ) 116.7 ° C. Dielectric anisotropy (Δε) 4.80 Refractive index anisotropy (Δn) 0.090 Threshold voltage (Vth) 1.88 V Response time (τ) 21.5 ms Here, the response time is a response time at the time of voltage application in which the rise time (τr) and the fall time (τd) are equal.

Next, (I-1) obtained in Example 1 was added to this (H).

[0341]

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When the nematic liquid crystal composition (M-1) was prepared by adding 20% of the compound (1), the maximum liquid crystal phase temperature (T _NI ) was 84.1 ° C. This (M-1) is 1
After being left at 50 ° C. for 20 hours, its T _NI was measured. Although the ultraviolet irradiation for 20 hours, changes in T _NI was observed. Next, when the voltage holding ratio of this composition was measured, it showed a sufficiently high value at the time of preparation, after heating and after irradiation with ultraviolet rays, similarly to the host liquid crystal (H).

Next, (M-1) was converted to a T cell having a cell thickness of 4.5 μm.
A liquid crystal element was prepared by filling in an N cell, and its electro-optical characteristics were measured. The results were as follows.

Nematic phase maximum temperature (T _NI ) 84.1 ° C. Dielectric anisotropy (Δε) 6.2 Threshold voltage (Vth) 1.49 V Response time (τ) 29.3 ms Dielectric of (M−1) The rate anisotropy greatly increases, and therefore, the threshold voltage is reduced by 20% or more as compared with (H).
When the number of fluorine molecules in the molecule increases, T _NI often decreases. However, T _NI of (M-1) is relatively high at 84.1 ° C., and (I-1) has relatively excellent liquid crystallinity. You can see that there is.

As described above, the compound of the general formula (I)
A) The temperature range of the nematic phase is wide, and b) Low threshold voltage enables low voltage driving. C) High speed response. D) High voltage holding ratio and sufficient active matrix driving. It is found to be very useful in preparing a suitable liquid crystal composition. (Example 11) Preparation of liquid crystal composition (2) A liquid crystal composition (M) having the following composition was prepared.

4% by weight of 4-ethoxy-1- (trans-4-propylcyclohexyl) benzene 3% by weight of 4-methylphenyl trans-4-pentylcyclohexanecarboxylate 3% by weight of trans-4-propylcyclohexanecarboxylic acid 4-ethoxyphenyl 3% by weight trans-4- (4-methylphenyl) -trans-4'-vinylbicyclohexane 3% by weight trans-4-butyl-trans-4'-propylbicyclohexane 4% by weight trans -4-pentyl-trans-4'-
Vinyl bicyclohexane 3% by weight of 4,4'-bis (3-buten-1-yl) bicyclohexane 4% by weight of 1- (4-propylphenyl) -2- (4-
Methylphenyl) ethyne 3% by weight of 1- (4-ethoxyphenyl) -2- (4-
Pentylphenyl) ethyne 3% by weight of 1,2-bis [4- (3-buten-1-yl) phenyl] ethyne 4% by weight of 1- (4-ethylphenyl) ethynyl-4-
(Trans-4-propylcyclohexyl) benzene 3% by weight of 4- (trans-4-pentylcyclohexyl) -4'-ethylbiphenyl 3% by weight of 4- (trans-4-propylcyclohexyl) -1-cyanobenzene 4% by weight % Of 4- [trans-4- (trans-1-propenyl) cyclohexyl] -1-cyanobenzene 3% by weight of 4- [trans-4- (3-buten-1-yl) cyclohexyl] -1-cyanobenzene 3% by weight 4'-pentyl-4-cyanobiphenyl 4% by weight 2- (4-cyanophenyl) -5-pentylpyrimidine 3% by weight 4-cyanophenyl 4-ethylbenzoate 3% by weight trans-4 3,4-difluorophenyl pentylcyclohexanecarboxylate 4% by weight of 3-fluoro-4 4-butylbenzoic acid The cyanophenyl 3 wt% of 4- (trans-3-penten-1-yl)
3,5-difluoro-4-cyanophenyl benzoate 3% by weight of trans-4- (3-fluoro-4-cyanophenyl) -trans-4 '-(3-methoxypropyl) bicyclohexane 3% by weight of trans- 4- (3,4-difluorophenyl) -trans-4'-ethylbicyclohexane 4% by weight of trans-4- (3,4-difluorophenyl) -trans-4'-vinylbicyclohexane 4% by weight of trans- 4- (3,4,5-trifluorophenyl) -trans-4'-propylbicyclohexane 3% by weight of trans-4- [2- (3,4,5-trifluorophenyl) ethyl] -trans-4 '-Propylbicyclohexane 3% by weight of 4- (trans-4-propylcyclohexyl) -4'-cyanobiphenyl 4% by weight of 4- (tolane 3-fluoro-4-cyanophenyl benzoate 3% by weight of 4 '-(trans-4-propylcyclohexyl) -3,4,5-trifluorobiphenyl 3% by weight of 1- (3 , 4,5-trifluorophenyl)
T _NI ethynyl-4- (trans-4-propyl-cyclohexyl) benzene This (M) is 75.0 ° C., [Delta] n is 0.1
42. 90% of this (M) and (I-1) obtained in Example 1

[0347]

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A liquid crystal composition (M-2) consisting of 10% of the above was prepared. T _NI of the (M-2) is 70.7 ° C., [Delta] n was 1.29.

(Comparative Example 1) (I-
Has a structure relatively similar to 1), but with 1-fluoro-2-
(A) which is a cyanonaphthalene derivative

[0350]

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Was added in the same amount (20%) to prepare a nematic liquid crystal composition (MA). 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 ) 105.2 ° C. Dielectric anisotropy (Δε) 4.15 Threshold voltage (Vth) 1.96 V (MA) T _NI is slightly higher than (M−1). Although it is higher, it was confirmed that (M-1) has a large Vth reduction effect because Δε is very large, and is improved by about 0.5 V.

[0353]

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. And has excellent compatibility with liquid crystal compounds or compositions that are currently widely used. In addition, (I): (a) enables low-voltage driving to reduce the threshold voltage; (b) lowers _TNI less than other fluorine-based liquid crystals; (c) enables high-speed response; and (d) maintains voltage It can be seen that the method is very useful for preparing a liquid crystal composition having a high rate and capable of sufficiently driving an active matrix.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Haruyoshi Takatsu 3-6-27 Nakahara, Higashiyamato-shi, Tokyo F-term (reference) 4H006 AA01 AB64 EA23 4H027 BA01 BC04 BD01 BD02 BD03 BD04 BD05 BD08 BD24 CB01 CB02 CC04 CD04 CL01 CL04 CM01 CM04 CN01 CN04 CP04 CQ01 CQ04 CT02 CT04 CW01 CW02 DE04 DK05 DM05

Claims (12)

[Claims] 1. A compound of the general formula (I) Wherein 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 substituted by a C ₁ -C ₇ alkoxyl group or one or more fluorine atoms. Ring A may be a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 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, naphthalene-2,6-diyl group,
Represents a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or a decahydronaphthalene-2,6-diyl group or a single bond, and L and M each independently represent-
_{CH 2 CH 2 -, - CH} 2 CH 2 CH 2 CH 2 -, - C (CH 3)
_{CH -, - CHC (CH 3} ) - or represents a single bond, when the ring B represents a single bond M represents a single bond. X ^{1 to} X ⁵ each independently represent a hydrogen atom or a fluorine atom,
At least one of X ¹ , X ² and X ³ represents a fluorine atom. A novel liquid crystalline compound which is a 2-fluoronaphthalene derivative represented by the following formula: 2. In the general formula (I), rings A, L and M
The compound according to claim 1, wherein represents a single bond. 3. A compound according to claim 1, wherein ring A in the formula (I) represents a trans-1,4-cyclohexylene group.
A compound as described. 4. In the general formula (I), ring A is 1,4-
The compound of claim 1, which represents a phenylene group. 5. The method according to claim 1, wherein in formula (I), at least one of L and M represents a single bond.
Described compounds 6. The method according to claim 1, wherein in the general formula (I), ring A represents a 2-fluoro-1,4-phenylene group or 2,6-difluoro-1,4-phenylene group, and M represents a single bond. Item 7. The compound according to Item 1. 7. The compound according to claim 1, wherein in the general formula (I), R represents a linear alkyl group having 1 to 7 carbon atoms.
A compound as described. 8. The method according to claim 1, wherein in the formula (I), R represents a linear alkenyl group having 1 to 7 carbon atoms.
4. The compound according to 4. 9. A liquid crystal composition containing the compound represented by the general formula (I) according to claim 1. 10. The liquid crystal composition according to claim 9, which is used for driving an active matrix. 11. A liquid crystal device comprising the liquid crystal composition according to claim 9 as a constituent element. 12. An active matrix driven liquid crystal display device using the liquid crystal composition according to claim 10.