JP6070110B2 - Compound with fluorinated naphthalene structure - Google Patents

Description

  The present invention relates to a compound having a fluorinated naphthalene structure which is useful as an organic electronic material, medical pesticide, or a liquid crystal display element material.

  Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type. Etc. The liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage. Further, the liquid crystal composition must have optimum values of dielectric anisotropy (Δε), refractive index anisotropy (Δn) and the like in accordance with individual display elements.

  In a TN type, STN type, or IPS type horizontal alignment type display, a liquid crystal composition having a positive Δε is used. In addition, a driving method in which a liquid crystal composition having a positive Δε is vertically aligned when no voltage is applied and a lateral electric field is applied is also reported. Thus, the importance of a liquid crystal composition having a positive Δε is increasing, and a compound having a larger positive Δε is required. On the other hand, an improvement in response speed is required in all driving systems, and in order to solve this problem, a liquid crystal composition having a viscosity lower than that of the current liquid crystal composition is required. In order to obtain a low-viscosity liquid crystal composition, it is effective to reduce the viscosity of each polar compound itself constituting the liquid crystal composition.

  In general, in order to obtain a compound having a low viscosity, a compound called a so-called straight ring system in which a ring structure is bonded without a linking group is preferred. However, straight-chain compounds having a positive Δε having three or more ring structures generally have high crystallinity, and there is a problem that crystals of the compound are precipitated when a liquid crystal composition containing the compound is cooled. When the compound is deposited from the liquid crystal composition, the physical property value of the liquid crystal composition is changed. Therefore, the compound added to the liquid crystal composition is required not to be separated or precipitated from a practical requirement for a long time. (Storage stability). In order to improve the storage stability, it is known that introduction of a linking group is effective, but there is a problem that the viscosity is significantly increased by introducing the linking group.

  For example, a straight-ring compound having the following fluorinated naphthalene structure (see Patent Document 1)

Shows a relatively low viscosity, but has a problem in storage stability. On the other hand, a compound having the following ether bond and fluorinated naphthalene structure (see Patent Document 2)

Has a higher storage stability than the above-mentioned straight ring compound, but has a problem of high viscosity.

US6468607B1 JP 2001-19649 A

  The problem to be solved by the present invention is to provide a compound exhibiting a positive Δε having both a low viscosity and a high storage stability, and also to provide a liquid crystal composition and a liquid crystal display device comprising the compound as a constituent member. is there.

  In order to solve the above problems, the present inventors have studied various compounds, and as a result, have completed the present invention.

  The present invention provides a general formula (1)

(Wherein R represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, one —CH ₂ — present in these groups or two or more not adjacent to each other) Each of —CH ₂ — may be independently replaced by —O—, —S—, —COO—, —OCO— or —CO—,
A ^{1 to} A ³ are each independently
(A) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - each independently is O- or -S- in May be replaced.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom or a chlorine atom.)
A group selected from the group consisting of:
Z ^{1 to} Z ³ are each independently —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF—, —C Represents ≡C—, —OCH ₂ —, —CH ₂ O— or a single bond,
X ¹ , X ³ and X ⁴ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom,
X ² represents a fluorine atom, a trifluoromethoxy group, a trifluoromethyl group or a cyano group,
Y represents a hydrogen atom or a fluorine atom,
l, n and m each independently represent 0 or 1, but l + m + n represents 1 to 3. In addition, a liquid crystal composition containing the compound and a liquid crystal display device using the liquid crystal composition are provided.

  The compound represented by the general formula (1) provided by the present invention has both positive Δε, low viscosity, and high storage stability.

  Therefore, by using the compound represented by the general formula (1) as a component of the liquid crystal composition, a liquid crystal composition exhibiting a positive Δε having a low viscosity and excellent storage stability can be obtained. For this reason, it is very useful as a component of the liquid crystal composition for liquid crystal display elements.

  In general formula (1), R is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce the viscosity, and alkyl having 1 to 5 carbon atoms. A group or an alkenyl group having 2 to 5 carbon atoms is particularly preferable. Moreover, it is preferable that it is linear.

Each of A ^{1 to} A ³ present independently is preferably a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group when importance is placed on a decrease in viscosity. , 4-cyclohexylene group is more preferable, and when importance is attached to an increase in Δε

It is preferable that when storage stability is important,

It is preferable that

Each of Z ^{1 to} Z ³ present independently is preferably —CF ₂ O—, —OCF ₂ —, —CF═CF— or a single bond when importance is placed on the decrease in viscosity, —CF ₂ O—, —OCF ₂ —, —OCH ₂ —, —CH ₂ O— or a single bond is more preferable, a single bond is particularly preferable, and when importance is placed on storage stability, —CF ₂ O—, —OCF ₂ — or —CH ₂ CH ₂ — is preferred, and —CH ₂ CH ₂ — is more preferred.

X ^1, X ³ and X ⁴ are each independently is preferably a fluorine atom in the case of emphasizing the increase of [Delta] [epsilon], X ¹ and X ³ it is more preferably a fluorine atom, X ³ is fluorine it is particularly preferably an atom, when emphasizing the viscosity is preferably X ¹ and X ⁴ is a hydrogen atom, and particularly preferably X ⁴ is a hydrogen atom.

X ² is preferably a trifluoromethyl group or a cyano group when emphasizing Δε, and is preferably a fluorine atom or a trifluoromethoxy group when emphasizing viscosity.

X ¹ , X ² and X ³ are preferably fluorine atoms when storage stability and Δε are important.

  Y is preferably a fluorine atom when Δε is important.

l + m + n is preferably 2 or 3 when emphasizing T _ni, and is preferably 1 or 2 when emphasizing viscosity.

  Note that the compound represented by the general formula (1) does not have a structure in which heteroatoms are directly bonded to each other.

  Specific examples of preferred compounds are shown below, but the present invention is not limited thereto. In general formula (1), each compound represented by the following general formula (1-1)-general formula (1-54) is preferable.

(In the formula, each R independently represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms.)
If the content of the compound represented by the general formula (1) is small in the liquid crystal composition of the present invention, the effect does not appear. Therefore, the lower limit value in the liquid crystal composition is 1% (% in the composition is% by mass). The same shall apply hereinafter), preferably 2%, more preferably 5%. Further, since a large content causes problems such as precipitation, the upper limit is preferably 50%, more preferably 30%, still more preferably 20%, and particularly preferably 10%. Although the compound represented by General formula (1) can also be used by 1 type, you may use 2 or more types of compounds simultaneously.

  In order to adjust the physical property value of the liquid crystal composition, a compound other than the compound represented by the general formula (1) may be used. In addition to a compound having a liquid crystal phase, a compound having no liquid crystal phase may be used as necessary. It can also be added.

  Thus, as a preferable representative example of the compound that can be used by mixing with the compound represented by the general formula (1), in the composition provided by the present invention, the general component (1) At least one compound represented by the formula (2), but it is preferable to contain at least one of the following second to sixth components as other components.

  That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (A1) to (A3).

In the above formula, R ^b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be replaced by —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C—. Any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to 2 carbon atoms 7 linear 1-alkenyl groups, linear 4-alkenyl groups having 4 to 7 carbon atoms, and alkyl groups having 1 to 5 carbon atoms substituted at the ends by alkoxy groups having 1 to 3 carbon atoms. preferable. Further, when asymmetric carbon is generated by branching, the compound may be optically active or racemic.

  Ring A, Ring B and Ring C may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. A good 1,4-phenylene group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, a tetrahydronaphthalene-2,6-optionally substituted by one or more fluorine atoms Diyl group, 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 -Represents a diyl group, but is substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or a fluorine atom. An optional naphthalene-2,6-diyl group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms is preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring A may be a trans-1,4-cyclohexylene group. Preferably, when ring C is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1,4-cyclohexylene groups. Preferably there is. In (A3), ring A is preferably a trans-1,4-cyclohexylene group.

L ^a , L ^b and L ^c are each a linking group and each independently represents a single bond, an ethylene group (—CH ₂ CH ₂ —), a 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—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CF═CF— or —C≡C— are preferred, and a single bond or an ethylene group is particularly preferred. Further, it is preferable that at least one of (A2) represents a single bond and at least two of (A3) represent a single bond.

  Ring Z is an aromatic ring and represents any one of the following general formulas (La) to (Lc).

In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom. In (La), at least one of Y ^a and Y ^b is preferably a fluorine atom, and in (Lb), At least one of Y ^{d to} Y ^f is preferably a fluorine atom, particularly preferably Y ^d is a fluorine atom, and in (Lc), at least one of Y ^h and Y ⁱ is a fluorine atom. In particular, Y ^h is more preferably a fluorine atom.

Terminal group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group, two or more carbon atoms substituted by fluorine atoms 2 or 3 alkoxy groups, 2 An alkyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, an alkenyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, or a carbon substituted by 2 or more fluorine atoms Although an alkenyloxy group having 2 or 3 atoms is represented, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.

  The third component is a so-called cyano p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (B1) to (B3).

In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be replaced by —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C—. Any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to 2 carbon atoms A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted at the terminal by an alkoxy group having 1 to 3 carbon atoms. preferable. Further, when asymmetric carbon is generated by branching, the compound may be optically active or racemic.

  Ring D, Ring E and Ring F may be each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. A good 1,4-phenylene group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, a tetrahydronaphthalene-2,6-optionally substituted by one or more fluorine atoms Diyl group, 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 -Represents a diyl group, but is substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or a fluorine atom. Preferred also good naphthalene-2,6-diyl group or 1-2 by fluorine atoms may be substituted 1,4-phenylene group. In particular, when ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring D may be a trans-1,4-cyclohexylene group. Preferably, when Ring F is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, Ring D and Ring E are trans-1,4-cyclohexylene groups. Preferably there is. In (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , ^Le and L ^f are each a linking group and each independently represents a single bond, an ethylene group (—CH ₂ CH ₂ —), a 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 —, —CH ₂ O— or —CH═NN═CH— represents a single bond, ethylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CF═CF— or —C≡C— are preferred, and a single bond, an ethylene group or —COO— is particularly preferred. In the general formula (B2), at least one of them preferably represents a single bond. In the general formula (B3), at least two of them preferably represent a single bond.

P ^b represents a cyano group.

  Ring Y is an aromatic ring and represents any one of the following general formulas (Ld) to (Lf).

In the formula, Y ^{k to} Y ^q each independently represent a hydrogen atom or a fluorine atom. In (Ld), at least one of Y ^k and Y ^l is preferably a fluorine atom, and in (Le) , Y ^{m to} Y ^o are preferably fluorine atoms, particularly Y ^m is more preferably a fluorine atom, and in (Lf), at least one of Y ^p and Y ^q is a fluorine atom. preferably there, it is further preferred, especially Y ^p is a fluorine atom.

  The fourth component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formulas (C1) to (C3).

In the above formula, R ^d and ^Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and may be a 3- to 6-membered ring. Any —CH ₂ — that may have a cyclic structure and is present in the group is —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or Any hydrogen atom present in the group may be substituted by —C≡C—, and may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl having 1 to 7 carbon atoms Group, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a terminal having carbon atoms A linear alkyl group having 1 to 5 carbon atoms substituted by 1 to 3 alkoxy groups is preferred, At least one of them 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 to 2 fluorine atoms, or 1,4-phenylene group optionally substituted by a methyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, substituted by 1 or 2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group, a 1,4-cyclohexenylene group optionally substituted by 1 to 2 fluorine atoms, a 1,3-dioxane-trans-2,5-diyl group, Represents a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, but in each compound, a transdecahydronaphthalene-trans-2,6-diyl group, one or more fluorine groups. A naphthalene-2,6-diyl group optionally substituted by an atom, a tetrahydronaphthalene-2,6-diyl group optionally substituted by one or two fluorine atoms, and may be substituted by a fluorine atom The number of 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably within one. The other ring is preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group. The total number of fluorine atoms present in ring G, ring H, ring I and ring J is preferably 2 or less, and preferably 0 or 1.

L ^g , L ^h and ^Li are each a linking group, each independently a single bond, an ethylene group (—CH ₂ CH ₂ —), a 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—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CF═CF—, —C≡C— or —CH═NN═CH— are preferred, and in general formula (C2), at least one of them is represented by general formula (C3 ), At least two of them preferably represent a single bond.

  The compounds represented by the general formulas (C1) to (C3) exclude the compounds represented by the general formulas (A1) to (A3) and the compounds represented by the general formulas (B1) to (B3).

  In the compounds represented by the general formulas (A1) to (A3), the general formulas (B1) to (B3), and the compounds represented by the general formulas (C1) to (C3), heteroatoms are directly bonded to each other. There is no structure.

  The fifth component is an optically active compound used to induce a helical structure in the liquid crystal composition. A compound having an asymmetric carbon atom is preferable, and a compound having a 1-methylheptyloxy group is more preferable.

  The sixth component is a compound having a polymerizable functional group that can be polymerized by ultraviolet irradiation or heating, which is added to improve the response speed or improve the orientation of the liquid crystal composition. The polymerizable group is preferably an acryloxy group or a methacryloxy group, and more preferably a methacryloxy group. Moreover, it is preferable to have 1 to 3 polymerizable functional groups, and it is more preferable to have two.

In the present invention, the compound represented by the general formula (1) can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
(Production method 1)
General formula (2)

(Wherein X ^{1 to} X ⁴ represent the same meaning as X ^{1 to} X ⁴ in the general formula (1)) can be produced based on the published patent publication 2004-91361.

  By reacting the compound represented by the general formula (2) with trifluoromethanesulfonic anhydride in the presence of a base, the general formula (3)

(Wherein ^X 1 to X ⁴ are the same as defined ^X 1 to X ⁴ in the general formula (1).) In the compound represented by the get it is possible.

  Any solvent can be used as long as it allows the reaction to proceed suitably. Ether solvents such as tetrahydrofuran and diethyl ether, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and the like A chlorinated solvent such as hexane, toluene or xylene is preferred, and dichloromethane or chloroform is more preferred. These solvents may be used alone or in combination.

  As the base, any base can be used as long as the reaction proceeds suitably. Nitrogen-containing aromatic bases such as pyridine or lutidine, aliphatic amines such as triethylamine or diisopropylamine are preferable, and pyridine is particularly preferable. .

  The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably −20 ° to 40 ° C., more preferably 0 ° C. to 30 ° C.

  Subsequently, by reacting the compound represented by the general formula (3) with potassium cyanide in the presence of a transition metal catalyst and various additives, the general formula (4)

(Wherein ^X 1 to X ⁴ are the same as defined ^X 1 to X ⁴ in the general formula (1).) In the compound represented by the get it is possible.

  Any transition metal catalyst may be used as long as the reaction proceeds smoothly. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphino) palladium dichloride ( II), palladium-based transition metal catalysts such as [1,1′-bis (diphenylphosphino) ferrocene] palladium (II), bis (dibenzylideneacetone) palladium (0), or bis (triphenylphosphine dichloride) Nickel-based transition metal catalysts such as nickel (II), bis (triphenylphosphine) nickel (II) dibromide, [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride are preferred, and tetrakis Triphenylphosphine palladium (0), palladium (II) acetate, disalt [1,1'-bis (diphenylphosphino) ferrocene] palladium (II), bis (triphenylphosphine) nickel (II) or dibromide bis (triphenylphosphine) nickel (II) is more preferable. Moreover, in order to accelerate | stimulate progress of reaction, you may add a phosphine-type ligand as needed.

  Any additive may be used as necessary as long as it allows the reaction to proceed smoothly, but carbonates such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, or zinc metal are preferred.

  The solvent may be any as long as it allows the reaction to proceed smoothly. However, an ether solvent such as diethyl ether or tetrahydrofuran, an aromatic solvent such as toluene or xylene, N, N-dimethylformamide, N, Amide solvents such as N, -dimethylacetamide or N-methylpyrrolidone, and nitrile solvents such as acetonitrile or propylonitrile are preferred, and N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide or acetonitrile is preferred. Further preferred.

  Any temperature can be used as long as the reaction proceeds smoothly, but the temperature is preferably from 0 ° C. to the reflux of the reaction solvent, more preferably from 60 ° C. to 140 ° C.

  Subsequently, the compound represented by the general formula (4) is reacted with a reducing agent, and then hydrolyzed with an acid, whereby the general formula (5)

(Wherein ^X 1 to X ⁴ are the same as defined ^X 1 to X ⁴ in the general formula (1).) In the compound represented by the get it is possible.

  Any reducing agent may be used as long as the reaction proceeds smoothly, but aluminum hydride reagents such as lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, diisobutylaluminum hydride, and the like can be used. Preferably, diisobutylaluminum hydride is more preferable.

  The acid used for the hydrolysis is preferably an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, and more preferably hydrochloric acid.

  The solvent may be any as long as it allows the reaction to proceed smoothly, but ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, chlorine solvents such as dichloromethane, chloroform and carbon tetrachloride, Aliphatic solvents such as hexane and heptane, and aromatic solvents such as toluene and xylene are preferred, and tetrahydrofuran, toluene and xylene are more preferred.

  The temperature may be any temperature as long as it allows the reaction to proceed smoothly, but is preferably −20 ° C. to the temperature at which the reaction solvent is refluxed, more preferably −10 ° C. to 30 ° C.

  Subsequently, by reacting the compound represented by the general formula (5) with a reducing agent, the general formula (6)

(Wherein ^X 1 to X ⁴ are the same as defined ^X 1 to X ⁴ in the general formula (1).) In the compound represented by the get it is possible.

  Any reducing agent may be used as long as the reaction proceeds smoothly, but borohydride reagents such as sodium borohydride, lithium borohydride, borane, lithium aluminum hydride, diisobutylaluminum hydride, hydrogen A method of using an aluminum hydride reagent such as sodium bis (2-methoxyethoxy) aluminum hydride, palladium / carbon, etc. in a hydrogen atmosphere is preferred. Sodium borohydride or bis (2-methoxyethoxy) aluminum hydride More preferably, sodium is used.

  Any solvent can be used as long as it allows the reaction to proceed smoothly. Ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, and tetrahydrofuran, and aromatic solvents such as toluene and xylene are preferred. More preferred is diethyl ether, tetrahydrofuran or toluene. In addition, when sodium borohydride or lithium borohydride is used as the reducing agent, alcohol solvents such as methanol, ethanol and isopropyl alcohol are also preferably added to the above solvent, and water is also preferably added as necessary.

  The temperature may be any temperature as long as the reaction proceeds smoothly, but is preferably −20 ° C. to the temperature until the solvent is refluxed, and more preferably 0 ° C. to 50 ° C.

  Then, general formula (7)

(In the formula, R, Y, A ^{1 to} A ³ , Z ^{1 to} Z ³ , l, n and m are R, Y, A ^{1 to} A ³ , Z ^{1 to} Z ³ , l in General Formula (1), n and m have the same meaning.) The compound represented by formula (8) is reacted with a base, reacted with a borate ester, and further reacted with an oxidizing agent.

(In the formula, R, Y, A ^{1 to} A ³ , Z ^{1 to} Z ³ , l, n and m are R, Y, A ^{1 to} A ³ , Z ^{1 to} Z ³ , l in General Formula (1), the same meaning as n and m) can be obtained.

  As the base, alkyl lithium reagents such as butyl lithium, sec-butyl lithium and tert-butyl lithium, and lithium amide reagents such as lithium diisopropylamide and lithium dibutylamide are preferable. When Y represents a hydrogen atom, it is more preferable to use sec-butyl lithium, tert-butyl lithium or lithium diisopropylamide among the above bases. When Y represents a fluorine atom, it is more preferable to use butyl lithium among the above bases. In addition, when using a base, if necessary, a reagent for stabilizing anion species generated in the system such as N, N, N ′, N′-tetramethylethylenediamine or hexamethylphosphoric triamide may be added. good.

  Any boric acid ester may be used as long as the reaction proceeds smoothly, but trimethyl borate, triisopropyl borate, and the like are preferable.

  As the oxidizing agent, hydrogen peroxide solution, peracids such as performic acid and peracetic acid are preferable, and hydrogen peroxide solution is more preferable.

  As the solvent, any solvent can be used as long as it allows the reaction to proceed smoothly. When reacting with a base and boric acid esters, ether solvents such as diethyl ether, tetrahydrofuran, tert-butyl methyl ether, toluene, Aromatic solvents such as xylene and aliphatic solvents such as hexane and heptane are preferred, and tetrahydrofuran or hexane is more preferred. When reacting with an oxidizing agent, ether solvents such as tetrahydrofuran and 1,4-dioxane, chlorine solvents such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane, aliphatic solvents such as hexane and heptane It is preferable to use tetrahydrofuran and hexane.

  The temperature may be any as long as it allows the reaction to proceed smoothly, but is preferably −78 ° C. to −20 ° C. when reacting with a base and a boric acid ester, and −78 ° C. to −78 ° C. More preferably, it is 40 degreeC. When making it react with an oxidizing agent, the temperature from 0 degreeC to a solvent recirculation | reflux is preferable, and it is still more preferable that it is 20 to 45 degreeC.

  Subsequently, the compound represented by the general formula (6) is reacted with the compound represented by the general formula (8) in the presence of triphenylphosphine and azodicarboxylic acid esters, thereby being represented by the general formula (1). A compound can be obtained.

  Any azodicarboxylic acid ester may be used as long as the reaction proceeds smoothly, but diethyl azodicarboxylate or diisopropyl azodicarboxylate is preferred, and diisopropyl azodicarboxylate is more preferred.

  Any solvent can be used as long as it allows the reaction to proceed smoothly. Ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, and tetrahydrofuran; aliphatic solvents such as hexane and heptane; toluene An aromatic solvent such as xylene is preferable, and tetrahydrofuran is more preferable.

  Any temperature can be used as long as the reaction proceeds smoothly, but it is preferably −40 ° C. to 40 ° C., more preferably −10 to 10 ° C.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.

  “%” In the compositions of the following examples and comparative examples means “% by mass”.

T _n−i represents a transition temperature between a nematic phase and an isotropic phase.

  The following abbreviations are used in compound descriptions.

THF: Tetrahydrofuran DMF: N, N-dimethylformamide Pr: n-propyl group Tf: trifluoromethanesulfonyl group (Example 1) (5,6,7-trifluoronaphthalen-2-yl)-[4- (trans- 4- (trans-4-propylcyclohexyl) cyclohexyl) -2,6-difluorophenyloxy] methane

(1-1) Under a nitrogen atmosphere, 5,6,7-trifluoro-2-naphthol (208 g, produced according to JP-A No. 2004-91361) and pyridine (125 g) were dissolved in dichloromethane (1000 mL) and ice-cooled. . A solution of trifluoromethanesulfonic anhydride (310 g) in dichloromethane (620 mL) was added at a rate such that the internal temperature did not exceed 15 ° C., and the mixture was stirred at room temperature for 7 hours. Under ice-cooling, 15% hydrochloric acid (700 mL) was added, and the organic layer was separated. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried by adding sodium sulfate. After the solvent was distilled off under reduced pressure, trifluoromethanesulfonic acid 5,6,7-trifluoronaphthalen-2-yl (297 g) was obtained as a transparent liquid by purification by silica gel column chromatography.
(1-2) Under a nitrogen atmosphere, trifluoromethanesulfonic acid 5,6,7-trifluoronaphthalen-2-yl (120 g) obtained in (1-1), potassium cyanide (47.3 g), bis (dibromide) A solution of (triphenylphosphine) nickel (II) (13.5 g), triphenylphosphine (9.5 g) and metallic zinc (2.4 g) suspended in acetonitrile (540 mL) was heated to 80 ° C. for 16 hours. Stir. After cooling to room temperature, water (300 mL) and toluene (200 mL) were added for liquid separation, and the organic layer was washed twice with water (200 mL). A 70% aqueous tert-butyl hydroperoxide solution (12 mL) was added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour. The organic layer was washed with saturated brine (200 mL) and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography and recrystallized from ethanol to obtain 2-cyano-5,6,7-trifluoronaphthalene (35.8 g).
(1-3) Under a nitrogen atmosphere, 2-cyano-5,6,7-trifluoronaphthalene (35.8 g) obtained in (1-2) was dissolved in toluene (700 mL). 5 mol / L diisobutylaluminum hydride / toluene solution (115 mL) was slowly added. After stirring at room temperature for 1 hour, 10% hydrochloric acid (200 mL) was added under ice cooling. The mixture is further stirred for 1 hour at room temperature and separated. The organic layer is washed with 10% hydrochloric acid (100 mL), saturated brine (100 mL) and saturated brine (150 mL), and the organic layer is passed through an alumina column. A crude toluene solution of 5,6,7-trifluoro-2-naphthaldehyde was obtained.
(1-4) Sodium borohydride (3.9 g) was dissolved in methanol (80 mL) and ethanol (80 mL), ice-cooled, and 5,6,7-trifluoro-2 obtained in (1-3) -The total amount of naphthaldehyde in toluene was added slowly. After stirring at room temperature for 3 hours, 10% hydrochloric acid (200 mL) was slowly added under ice cooling, and the mixture was stirred at room temperature for 45 minutes. The organic layer was separated, washed with a saturated aqueous sodium hydrogen carbonate solution (200 mL) and saturated brine (200 mL), and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by alumina column chromatography and then recrystallized from toluene to obtain 5,6,7-trifluoro-2-hydroxymethylnaphthalene (24.4 g).
(1-5) Under a nitrogen atmosphere, a solution of metal magnesium (5.5 g) suspended in THF (5 mL) and 3,5-difluorobromobenzene (41.5 g) dissolved in THF (120 mL) was gently Was added at a rate of reflux and stirred at 40 ° C. for 45 minutes. Subsequently, a solution of 4- (trans-4-propylcyclohexyl) cyclohexanone (39.8 g) dissolved in THF (85 mL) was added at 40 ° C., and the mixture was stirred at room temperature for 1 hour. The reaction mixture was gently added to 10% hydrochloric acid (120 mL) cooled to 5 ° C. with stirring, and toluene (160 mL) was added for extraction. The organic layer was washed with saturated brine (120 mL), dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to give crude 3,5-difluoro-4- (1-hydroxy-4- (4). -Trans-propylcyclohexyl) cyclohexyl) benzene (62.5 g) was obtained.
(1-6) Crude 3,5-difluoro-4- (1-hydroxy-4- (trans-4-propylcyclohexyl) cyclohexyl) benzene (62.5 g) obtained in (1-5) and p-toluene A solution obtained by dissolving sulfonic acid monohydrate (1.7 g) in toluene (300 mL) was refluxed, and stirred for 5 hours while removing generated water using a Dean-Stark apparatus. The mixture was allowed to cool, and water (150 mL) was added for liquid separation, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (150 mL) and saturated brine (150 mL), and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and the resulting residue was purified by alumina column chromatography to obtain crude 3,5-difluoro-4- (4- (trans-4-propylcyclohexyl) -1-cyclohexenyl) benzene. (64.1 g) was obtained.
(1-7) Crude 3,5-difluoro-4- (4- (trans-4-propylcyclohexyl) -1-cyclohexenyl) benzene (64.1 g) and 5 wt% palladium obtained in (1-6) / A solution of carbon (3.0 g) in toluene (200 mL) and ethanol (100 mL) was placed in an autoclave and stirred at 40 ° C. for 5 hours in a hydrogen atmosphere (0.5 MPa). Palladium / carbon was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude 3,5-difluoro-4- (4- (trans-4-propylcyclohexyl) -1-cyclohexyl) benzene (64.3 g). Obtained.
(1-8) Crude 3,5-difluoro-4- (4- (trans-4-propylcyclohexyl) cyclohexyl) benzene (64.3 g) and tert-obtained in (1-7) under a nitrogen atmosphere Butyloxypotassium (2.0 g) was dissolved in DMF (300 mL) and stirred at 70 ° C. for 3 hours. After allowing to cool, toluene (300 mL) and water (300 mL) are added and the layers are separated, and the organic layer is washed with water (300 mL) and saturated brine (300 mL), dried over anhydrous sodium sulfate, and dried. Was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, distilled under reduced pressure (0.7 mmHg, boiling point 171 to 174 ° C.), and recrystallized from ethanol to obtain 3,5-difluoro-4- (trans-4- (trans-4- (trans- 4-Propylcyclohexyl) cyclohexyl) benzene (43.5 g) was obtained.
(1-9) Under a nitrogen atmosphere, 3,5-difluoro-4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) benzene (25.0 g) obtained in (1-8) was added to THF. The solution was dissolved in (250 mL), cooled to −40 ° C., 1.6 mol / L butyl lithium / hexane solution (55 mL) was slowly added, and the mixture was further stirred at −40 ° C. for 30 minutes. Subsequently, trimethyl borate (9.7 g) was slowly added at −40 ° C., and then the temperature was slowly raised to room temperature. After adding water (5 mL), 10% hydrochloric acid (60 mL) was added and liquid-separated, and saturated sodium hydrogencarbonate aqueous solution (50 mL) was added. Subsequently, a 30% aqueous hydrogen peroxide solution (10.6 g) was slowly added at room temperature, followed by stirring at 45 ° C. for 30 hours. The mixture was allowed to cool to room temperature, 10% aqueous sodium sulfite solution (100 mL) was added, and the mixture was partitioned. Toluene (75 mL) and THF (75 mL) were added to the aqueous layer for extraction, and the combined organic layer was saturated brine (200 mL). And dried with anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and then recrystallized from a mixed solvent of hexane / toluene to give 2,6-difluoro-4- [trans-4- (trans-4-propylcyclohexyl). ) Cyclohexyl] phenol (14.9 g) was obtained.
(1-10) 5,6,7-trifluoro-2-hydroxymethylnaphthalene obtained in (1-4) under nitrogen atmosphere (8.0 g), 2 obtained in (1-9) , 6-Difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenol (14.9 g) and triphenylphosphine (10.9 g) were dissolved in THF (60 mL), and the azo compound was cooled under ice-cooling. Diisopropyl dicarboxylate (8.0 g) was slowly added, followed by stirring at room temperature for 1 hour. After adding water (5 mL), the organic solvent was distilled off under reduced pressure, methanol (100 mL), water (50 mL) and a 70% aqueous tert-butyl hydroperoxide solution (2 g) were added, and the mixture was stirred at room temperature for 3 hours. The precipitate was taken out by filtration, dried under reduced pressure, purified by silica gel column chromatography, and recrystallized from a mixed solvent of acetone and toluene to give (5,6,7-trifluoronaphthalen-2-yl)-[4 -(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2,6-difluorophenyloxy] methane (16.4 g) was obtained.
Phase transition: Cr 128 N 233 Iso
MS m / z: 530 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.04 (1H, d, J = 8.7 Hz), 7.83 (1H, s), 7.64 (1H, d, J = 8) .5 Hz), 7.41-7.36 (1 H, m), 6.74 (2 H, d, J = 9.6 Hz), 5.25 (2 H, s), 2.35 (1 H, tt, J ₁ = 3.2 Hz, J ₂ = 12.1 Hz), 1.89-1.70 (8H, m), 1.33-1.26 (4H, m), 1.16-1.11 (6H, m), 1.06-0.94 (3H, m), 0.89-0.81 (5H, m)
Example 2 (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (trans-4-propylcyclohexyl) phenyl) phenyloxy] Synthesis of methane

(2-1) 4-nitro-2,6-difluorophenol (41.8 g), tetrakis (triphenylphosphine) palladium (0) (4.6 g), 2 mol / L aqueous potassium carbonate solution (200 mL) under nitrogen atmosphere And ethanol (200 mL) were mixed and heated to 60 ° C., and a solution of 2-fluoro-4- (trans-4-propylcyclohexyl) phenylboronic acid (58.1 g) dissolved in ethanol (180 mL) was slowly added. It was. After further stirring at 60 ° C. for 15 hours, the mixture was allowed to cool, and toluene (200 mL) and 10% hydrochloric acid (300 mL) were added to separate the layers. Toluene (200 mL) was added to the aqueous layer for extraction, and the combined organic layer was washed with saturated brine (300 mL), dried over anhydrous sodium sulfate. After the organic solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and then recrystallized from a mixed solvent of hexane and toluene, whereby 2,6-difluoro-4- [2-fluoro-4- (trans-4 -Propylcyclohexyl) phenyl] phenol (45.8 g) was obtained.
(2-2) 5,6,7-trifluoro-2-hydroxymethylnaphthalene obtained in (1-4) under nitrogen atmosphere (8.0 g), 2,6 obtained in (2-1) -Difluoro-4- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] phenol (13.1 g) and triphenylphosphine (11.4 g) were dissolved in THF (80 mL), and the azo compound was cooled under ice-cooling. Diisopropyl dicarboxylate (8.4 g) was added slowly. After stirring at room temperature for 1 hour, water (5 mL) was added and the organic solvent was distilled off under reduced pressure. Hexane (50 mL), methanol (100 mL), water (50 mL) and 70% aqueous tert-butyl hydroperoxide (0.4 g) were added to the resulting residue, and the mixture was stirred at room temperature for 2 hours. The precipitate was taken out by filtration, dried under reduced pressure, purified by silica gel column chromatography, and recrystallized from a mixed solvent of acetone and toluene to give (5,6,7-trifluoronaphthalen-2-yl)-[2,6 -Difluoro-4- (2-fluoro-4- (trans-4-propylcyclohexyl) phenyl) phenyloxy] methane (13.2 g) was obtained.
Phase transition: Cr 129 N 204 Iso
MS m / z: 542 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.07 (1H, d, J = 8.6 Hz), 7.85 (1H, s), 7.66 (1H, d, J = 8) .7 Hz), 7.43-7.38 (1H, m), 7.29-7.14 (1 H, m), 7.10 (2H, d, J = 8.4 Hz), 7.05-6 .97 (2H, m), 5.35 (2H, s), 2.49 (1H, tt, J ₁ = 3.4 Hz, J ₂ = 12.2 Hz), 1.93-1.86 (4H, m), 1.49-1.19 (7H, m), 1.10-1.00 (2H, m), 0.91 (3H, t, J = 7.1 Hz)
Example 3 Production of (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyloxy] methane

(5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) was carried out in the same manner as described in Examples 1 and 2. ) Phenyloxy] methane (10.1 g) was obtained.
MS m / z: 448 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.05 (1H, d, J = 8.8 Hz), 7.83 (1H, s), 7.64 (1H, d, J = 8) .8 Hz), 7.41-7.36 (1 H, m), 6.78 (2 H, d, J = 9.2 Hz), 5.17 (2 H, s), 2.38 (1 H, tt, J ₁ = 3.0 Hz, J ₂ = 12.3 Hz), 1.86-1.83 (4H, m), 1.38-1.24 (5H, m), 1.22-1.17 (2H, m), 1.06-0.96 (2H, m), 0.89 (3H, t, J = 7.1 Hz)
Example 4 (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (4- (trans-4-propylcyclohexyl) phenyl) Phenyl) phenyloxy] methane production

(4-1) Under dry nitrogen, 5,6,7-trifluoro-2-hydroxymethylnaphthalene (10.0 g) obtained in (1-4), 4-bromo-2,6-difluorophenol (9 0.8 g) and triphenylphosphine (13.6 g) were dissolved in THF (50 mL), ice-cooled, and diisopropyl azodicarboxylate (10.0 g) was slowly added. After stirring at room temperature for 1 hour, water (5 mL) was added, and then the organic solvent was distilled off under reduced pressure. Hexane (50 mL), methanol (100 mL), water (50 mL) and 70% aqueous tert-butyl hydroperoxide (5 g) were added to the resulting residue, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with water (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, (5,6,7-trifluoronaphthalen-2-yl)-(4-bromo-2,6-difluorophenyloxy) methane (18) was purified by silica gel column chromatography. .2 g) was obtained.
(4-2) 4- (trans-4-propylcyclohexyl) bromobenzene (36.6 g), 2 mol / L aqueous potassium carbonate solution (130 mL), tetrakis (triphenylphosphine) palladium (0) (4. 5 g) and ethanol (180 mL) were mixed and heated to 60 ° C., a solution of 3-fluorophenylboronic acid (20.0 g) dissolved in ethanol (60 mL) was slowly added, and the mixture was stirred at 60 ° C. for 6 hours. . The mixture was allowed to cool, toluene (200 mL) and water (300 mL) were added, and the mixture was separated. The organic layer was washed with water (300 mL) and saturated brine (300 mL), and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography and recrystallized from a mixed solvent of ethanol and acetone to give 3- [4- (trans-4-propylcyclohexyl) phenyl] fluorobenzene (29.9 g). )
(4-3) 3- [4- (trans-4-propylcyclohexyl) phenyl] fluorobenzene (29.9 g) obtained in (4-2) was dissolved in THF (300 mL) under a nitrogen atmosphere, The mixture was cooled to 60 ° C., and 1.0 mol / L sec-butyllithium / hexane solution (120 mL) was slowly added. After stirring at −60 ° C. for 1 hour, triisopropyl borate (24.7 g) was added at −60 ° C., and the temperature was slowly raised to room temperature. Water (10 mL) was added, 10% hydrochloric acid (100 mL) was added, and the mixture was separated. The organic layer was washed with saturated brine (300 mL) and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure to obtain crude 2-fluoro-4- [4- (trans-4-propylcyclohexyl) phenyl] phenylboronic acid (33.2 g).
(4-4) (5,6,7-trifluoronaphthalen-2-yl)-(4-bromo-2,6-difluorophenyloxy) methane (18) obtained in (4-1) under a nitrogen atmosphere. 2 g), 2 mol / L potassium carbonate aqueous solution (45 mL), tetrakis (triphenylphosphine) palladium (0) (2.6 g) and THF (90 mL) are mixed, heated to 60 ° C., and (4-3) A solution of the obtained 2-fluoro-4- [4- (trans-4-propylcyclohexyl) phenyl] phenylboronic acid (16.9 g) in THF (90 mL) was slowly added, and further at 60 ° C. Stir for 10 hours. The mixture was allowed to cool, toluene (300 mL) and water (200 mL) were added, and the mixture was separated. The organic layer was washed with water (300 mL) and saturated brine (300 mL), and dried over anhydrous sodium sulfate. After distilling off the organic solvent under reduced pressure, the residue was purified by silica gel column chromatography and recrystallized from a mixed solvent of acetone and toluene to obtain (5,6,7-trifluoronaphthalen-2-yl)-[2, 6-Difluoro-4- (2-fluoro-4- (4- (trans-4-propylcyclohexyl) phenyl) phenyl) phenyloxy] methane (49.5 g) was obtained.
MS m / z: 618 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.05 (1H, d, J = 8.7 Hz), 7.81 (1H, s), 7.64 (1H, d, J = 8) .5 Hz), 7.41-7.36 (3 H, m), 7.27 (1 H, t, J = 8.0 Hz), 7.24 (2 H, d, J = 8.8 Hz), 7.06 −6.98 (2H, m), 6.75 (2H, d, J = 9.6 Hz), 5.11 (2H, s), 2.49 (1H, tt, J1 = 2.8 Hz, J2 = 12.0 Hz), 1.93-1.86 (4H, m), 1.49-1.19 (7H, m), 1.11-1.00 (2H, m), 0.91 (3H, t, J = 7.6 Hz)
Example 5 Production of (5,6,7-trifluoronaphthalen-2-yl)-[2-fluoro-4- (4-propylphenyl) phenyloxy] methane

(5,6,7-trifluoronaphthalen-2-yl)-[2-fluoro-4- (4-propylphenyl) phenyloxy] was carried out in the same manner as described in Examples 1 to 4. Methane (5.1 g) was obtained.
MS m / z: 424 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.05 (1H, d, J = 8.7 Hz), 7.81 (1H, s), 7.64 (1H, d, J = 8) .5Hz), 7.43 (2H, d, J = 8.4 Hz), 7.41-7.36 (2H, m), 7.27 (2H, d, J = 8.0 Hz), 7.07 (1H, d, J = 7.9 Hz), 6.86-6.77 (2H, m), 5.07 (2H, s), 2.64 (2H, t, J = 7.6 Hz), 1 .72-1.63 (2H, m), 0.97 (3H, t, J = 7.2 Hz)
Reference Example 1 Production of (5,6,7-trifluoronaphthalene-2-oxy)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] methane

(6-1) By carrying out the same method as described in Example 1, 3,5-difluoro-4- (trans-4-propylcyclohexyl) benzene (36.8 g) was obtained.
(6-2) Under a nitrogen atmosphere, 3,5-difluoro-4- (trans-4-propylcyclohexyl) benzene (36.8 g) obtained in (6-1) was dissolved in THF (180 mL), The solution was cooled to −40 ° C., and a 1.6 mol / L butyl lithium / hexane solution (106 mL) was slowly added. After further stirring at −40 ° C. for 1 hour, DMF (14.7 g) was slowly added, and then the temperature was slowly raised to room temperature. 10% Hydrochloric acid (150 mL) and toluene (150 mL) were added for liquid separation, and the aqueous layer was extracted with toluene (100 mL). The combined organic layer was washed with saturated brine (300 mL), and anhydrous sodium sulfate was added. In addition, it was dried. The organic solvent was distilled off under reduced pressure to obtain crude 2,6-difluoro-4- (trans-4-propylcyclohexyl) benzaldehyde (40.5 g).
(6-3) 2,6-difluoro-4- (trans-4-propylcyclohexyl) benzaldehyde (15.0 g) obtained in (6-2), 10% aqueous sodium hydroxide (10 mL) and ethanol ( 150 mL), ice-cooled, sodium borohydride (1.3 g) was slowly added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was added to 10% hydrochloric acid (300 mL), and toluene (150 mL) was added for liquid separation. Toluene (100 mL) was added to the aqueous layer for extraction, and the combined organic layer was washed with saturated aqueous sodium hydrogen carbonate solution (150 mL) and saturated brine (150 mL), and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure to obtain crude 2,6-difluoro-4- (trans-4-propylcyclohexyl) benzyl alcohol (14.4 g).
(6-4) 5,6,7-trifluoro-2-naphthol (10.6 g, produced according to JP-A No. 2004-91361) under the nitrogen atmosphere, 2,6-obtained in (6-3) Difluoro-4- (trans-4-propylcyclohexyl) benzyl alcohol (14.4 g) and triphenylphosphine (17.1 g) were dissolved in THF (70 mL), cooled to −10 ° C., and diisopropyl azodicarboxylate (11 .9 g) was added slowly. After further stirring at room temperature for 1 hour, water (5 mL) was added and the organic solvent was distilled off under reduced pressure. Hexane (150 mL), methanol (100 mL), water (50 mL) and 70% tert-butyl hydro hydrate were obtained. Peroxide (3 g) was added and stirred at room temperature for 2 hours. The organic layer was separated, washed with water (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and then recrystallized from a mixed solvent of acetone and ethanol to obtain (5,6,7-trifluoronaphthalene-2-oxy)-[2 , 6-Difluoro-4- (trans-4-propylcyclohexyl) phenyl] methane (13.6 g) was obtained.
MS m / z: 448 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 8.03 (1H, d, J = 9.2 Hz), 7.67 (1H, s,), 7.49-7.47 (1H, m), 7.38-7.33 (1H, m), 6.64 (2H, dd, J1 = 5.6 Hz, J2 = 9.0 Hz), 5.07 (s, 2H), 2.42 ( 1H, tt, J1 = 3.2 Hz, J2 = 12.4 Hz), 1.86-1.84 (4H, m), 1.45-1.17 (7H, m), 1.08-0.99 (2H, m), 0.90 (3H, t, J = 7.2 Hz)
Reference Example 2 Production of 5,6,7-trifluoro-2- [3-fluoro-4- (4-propylphenyl) phenyl] naphthalene

By carrying out in the same manner as described in Examples 1 to 4, 5,6,7-trifluoro-2- [3-fluoro-4- (4-propylphenyl) phenyl] naphthalene (50.1 g) was obtained. Obtained.
MS m / z: 394 [M ⁺ ]
Example 6 Preparation of Liquid Crystal Composition-1
Host liquid crystal composition (H) having the following composition

Was prepared. Here, the physical property values of (H) are as follows.

Nematic phase upper limit temperature (T _ni ): 117.2 ° C
Dielectric anisotropy (Δε): 4.38
Refractive index anisotropy (Δn): 0.0899
Viscosity (η ₂₀ ): 20.3 mPa · s
80% of the base liquid crystal (H) and (5,6,7-trifluoronaphthalen-2-yl)-[4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) obtained in Example 1 ) -2,6-difluorophenyloxy] methane 20% liquid crystal composition (MA) was prepared. The physical properties of this composition are as follows.

T _ni : 142.8 ° C
Δε: 6.46
Δn: 0.0989
η ₂₀ : 31.4 mPa · s
As an effect of adding (5,6,7-trifluoronaphthalen-2-yl)-[4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2,6-difluorophenyloxy] methane, T _{ni is} increased significantly (extrapolation T _ni = 245.1 ° C.), Δε is increased positively (extrapolation Δε = 14.8), and η ₂₀ is not increased too much (extrapolation η ₂₀ = 75.9 mPa · s) Moreover, since the prepared liquid crystal composition (MA) maintained the uniform nematic liquid crystal state for more than one month at room temperature, it turned out that high storage stability is shown.
(Example 7) Preparation of liquid crystal composition-2
The base liquid crystal (H) 80% and the (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (trans- A liquid crystal composition (MB) comprising 20% of 4-propylcyclohexyl) phenyl) phenyloxy] methane was prepared. The physical properties of this composition are as follows.

T _ni : 134.9 ° C
Δε: 8.04
Δn: 0.1157
η ₂₀ : 34.5 mPa · s
Effect of addition of (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (trans-4-propylcyclohexyl) phenyl) phenyloxy] methane _Tni is extremely increased (extrapolation T _ni = 205.6 ° C.), Δε is increased positively (extrapolation Δε = 22.7), and the viscosity is relatively difficult to increase (extrapolation η ₂₀ = 91.3 mPa · s). Moreover, since the prepared liquid crystal composition (MB) maintained the uniform nematic liquid crystal state for more than one month at room temperature, it turned out that it shows high storage stability.
Example 8 Preparation of Liquid Crystal Composition-3
Base liquid crystal (H) 80% and (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyloxy obtained in Example 3 A liquid crystal composition (M-C) composed of 20% methane was prepared. The physical properties of this composition are as follows.

T _ni : 111.2 ° C
Δε: 8.12
Δn: 0.1003
η ₂₀ : 22.9 mPa · s
As an effect of the addition of (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyloxy] methane, T _ni is not significantly reduced. (Extrapolation T _ni = 87.1 ° C.), Δε was increased positively (extrapolation Δε = 23.1), and the viscosity was not increased (extrapolation η ₂₀ = 33.5 mPa · s). Moreover, since the prepared liquid crystal composition (MC) maintained the uniform nematic liquid crystal state for more than one month at room temperature, it turned out that it shows high storage stability.
Example 9 Preparation of Liquid Crystal Composition-4
90% of the base liquid crystal (H) and (5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (4-) obtained in Example 4 A liquid crystal composition (MD) comprising 10% of (trans-4-propylcyclohexyl) phenyl) phenyl) phenyloxy] methane was prepared. The physical properties of this composition are as follows.

T _ni : 133.8 ° C
Δε: 6.71
Δn: 0.1106
η ₂₀ : 30.3 mPa · s
(5,6,7-trifluoronaphthalen-2-yl)-[2,6-difluoro-4- (2-fluoro-4- (4- (trans-4-propylcyclohexyl) phenyl) phenyl) phenyloxy] As an effect of the addition of methane, T _ni is significantly increased (extrapolation T _ni = 283.5 ° C.), Δε is increased positively (extrapolation Δε = 27.7), and the viscosity is relatively difficult to increase ( Extrapolation η ₂₀ = 120.1 mPa · s). Moreover, since the prepared liquid crystal composition (MD) maintained the uniform nematic liquid crystal state for more than one month at room temperature, it turned out that it shows high storage stability.
Example 10 Preparation of Liquid Crystal Composition-5
Base liquid crystal (H) 85% and (5,6,7-trifluoronaphthalen-2-yl)-[2-fluoro-4- (4-propylphenyl) phenyloxy] methane 15% obtained in Example 5 A liquid crystal composition (ME) comprising: The physical properties of this composition are as follows.

T _ni : 110.2 ° C.
Δε: 6.57
Δn: 0.1175
η ₂₀ : 23.2 mPa · s
As an effect of the addition of (5,6,7-trifluoronaphthalen-2-yl)-[2-fluoro-4- (4-propylphenyl) phenyloxy] methane, T _ni is slightly lowered (extrapolated T _ni It was found that Δε was increased positively (extrapolation Δε = 19.0) and the viscosity was hardly increased (extrapolation η ₂₀ = 39.9 mPa · s). Moreover, since the prepared liquid crystal composition (ME) maintained the uniform nematic liquid crystal state for more than one month at room temperature, it turned out that it shows high storage stability.
Reference Example 3 Preparation of Liquid Crystal Composition-6
Base liquid crystal (H) 90% and (5,6,7-trifluoronaphthalene-2-oxy)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] obtained in Example 5 A liquid crystal composition (MF) composed of 10% methane was prepared. The physical properties of this composition are as follows.

T _ni : 109.3 ° C
Δε: 6.41
Δn: 0.0914
η ₂₀ : 26.3 mPa · s
As an effect of the addition of (5,6,7-trifluoronaphthalene-2-oxy)-[2,6-difluoro-4- (trans-4-propylcyclohexyl) phenyl] methane, T _ni is greatly decreased ( It was found that extrapolation T _ni = 37.8 ° C., Δε was increased positively (extrapolation Δε = 24.7), and the viscosity was greatly increased (extrapolation η ₂₀ = 80.7 mPa · s). Moreover, when the prepared liquid crystal composition (ME) was stored at room temperature for 3 days, it was found that the storage stability was poor because the precipitation of crystals was confirmed.
Reference Example 4 Preparation of liquid crystal composition-7
A liquid crystal composition comprising 90% of the base liquid crystal (H) and 10% of 5,6,7-trifluoro-2- [3-fluoro-4- (4-propylphenyl) phenyl] naphthalene obtained in Reference Example 2. (MF) was prepared. The physical properties of this composition are as follows.

T _ni : 119.6 ° C
Δε: 6.15
Δn: 0.1137
η ₂₀ : 23.8 mPa · s
As an effect of addition of 5,6,7-trifluoro-2- [3-fluoro-4- (4-propylphenyl) phenyl] naphthalene, T _n−i is slightly increased (extrapolation T _ni = 140.8). ° C), Δε can be positively increased (extrapolation Δε = 22.1). When the prepared liquid crystal composition (MF) was stored at room temperature for 2 weeks, crystals were precipitated, indicating that it showed low storage stability.

  By comparing Example 8 with Reference Example 3 and Reference Example 4, it can be seen that the compound of the present invention has an extremely high effect of reducing the viscosity while maintaining high storage stability as compared with the reference compound.

Claims (10)

General formula (1)

(Wherein R represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, one —CH ₂ — present in these groups or two or more not adjacent to each other) Each of —CH ₂ — may be independently replaced by —O—, —S—, —COO—, —OCO— or —CO—,
A ^{1 to} A ³ are each independently
(A) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - each independently is O- or -S- in May be replaced.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom or a chlorine atom.)
A group selected from the group consisting of:
Z ^{1 to} Z ³ are each independently —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF—, —C Represents ≡C—, —OCH ₂ —, —CH ₂ O— or a single bond,
X ¹ , X ³ and X ⁴ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom,
X ² represents a fluorine atom, a trifluoromethoxy group, a trifluoromethyl group or a cyano group,
Y represents a hydrogen atom or a fluorine atom,
l, n and m each independently represent 0 or 1, but l + m + n represents 1 to 2 . ) A compound represented by The compound of Claim 1 in which Y represents a fluorine atom in General formula (1). The compound according to claim 1 or 2, wherein in the general formula (1), X ⁴ represents a hydrogen atom. In the general formula (1), A ^{1 to} A ^{3 present} are each independently any of the following groups:

The compound according to any one of claims 1 to 3 , which represents In the general formula (1), there is ^Z 1 to Z ³ is _-CH 2 CH ₂ - or A compound according to any one of claims 1 to 3 represents a single bond. The compound according to any one of claims 1 to 5, wherein in the general formula (1), X ² represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group. The compound as described in any one of Claims 1-6 in which X < ¹ > and X < ³ > represent a hydrogen atom or a fluorine atom in General formula (1). The compound according to any one of claims 1 to 7, wherein in the general formula (1), Z ¹ present represents -CH ₂ CH _2- , and Z ² and Z ³ represent a single bond. The compound according to any one of claims 1 to 7, wherein in the general formula (1), Z ^{1 to} Z ³ present each represent a single bond. In the general formula (1), compound according to any one of claims 1-9 in which X ¹ to X ³ that is present both represent fluorine atoms.