JP2013103897A - Azobenzene derivative, and liquid crystal composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition for providing a material realizing large refractive index anisotropy (Δn) as well as the compound being a constituting member, and to provide a liquid crystal display element and cholesteric liquid crystal display element using the liquid crystal composition.SOLUTION: There are provided a compound represented by general formula (1) which is an acetylene compound having an azobenzene site and tetra-hydronaphthalene structure, a liquid crystal composition containing the compound, and an liquid crystal display element using the liquid crystal composition, and a compound represented by general formula (4) which is used for a manufacturing method of the compound represented by general formula (1) and is a raw material using the manufacturing method.

Description

  The present invention relates to a compound having both an azobenzene structure and a biarylacetylene structure useful as an organic electronic material, medical pesticide, particularly a nematic liquid crystal material for electro-optical liquid crystal display, and a liquid crystal composition comprising the same, and a liquid crystal composition using the same The present invention relates to a liquid crystal display element.

  Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, as well as watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment (VA: vertical alignment) type using TFT (thin film transistor), and IPS (inside).・ Plain switching type. In recent years, in these liquid crystal display elements, there is a tendency to achieve higher-speed driving by narrowing the cell gap (d) of the liquid crystal cell. Here, there is a constraint that the value (retardation) of the product (d × Δn) of the cell gap and the refractive index anisotropy (Δn) must be optimized. For this reason, if the cell gap is narrowed (d is decreased), the value of Δn must be increased. Thus, it is necessary to increase the Δn value of the liquid crystal composition, and a liquid crystal compound having a larger Δn value than the existing liquid crystal compounds is demanded.

  On the other hand, development of a cholesteric liquid crystal display element is underway as a new display method. A polarizing plate is required to configure the conventional display element described above, and a color filter is required to realize color display, but the presence of the polarizing plate not only reduces the light use efficiency, The viewing angle characteristics are adversely affected, and the presence of a color filter has a problem that the light use efficiency is lowered. In contrast, cholesteric liquid crystal display elements display light by selectively reflecting light having a wavelength corresponding to the helical pitch of cholesteric liquid crystal from circularly polarized light components contained in external light, eliminating the need for polarizing plates and color filters. The drawbacks of the conventional liquid crystal display element can be improved.

  In a cholesteric liquid crystal display element, a selective reflection state in a planar state in which the spiral axis is usually perpendicular to the substrate is used. At this time, it is known that the half-value width (Δλ) of the selectively reflected light is represented by a product (Δn × P) of Δn and a natural pitch (P). In order to realize a bright display, a large Δn is used. The compound which has is required. Therefore, development of a liquid crystal compound exhibiting a larger Δn value is also strongly desired for a liquid crystal composition for a cholesteric liquid crystal display element.

  A typical example of a liquid crystal compound exhibiting a large Δn value is a tolan compound. The compound represented by the formula (A) has a Δn value of 0.178 (Patent Document 1). The value of Δn can generally be increased by expanding the conjugated system in the molecular structure in the molecular long axis direction. For this reason, a compound represented by the formula (B) in which an aromatic ring is introduced into the compound represented by the formula (A) to further increase Δn was developed, and Δn showed 0.384 (Patent Document 2). ).

  Further, an azine-based compound represented by the formula (C) conjugated in a wide range has been developed, and this compound has Δn of 0.340 (Patent Document 3).

  However, even these conventionally developed compounds are insufficient to meet the above-mentioned demands, and it has been demanded to meet the demand for further higher Δn.

  Both the azobenzene structure and the tolan structure are known as structures exhibiting a large Δn, and a compound represented by the formula (D) has been reported as a material having both these structures (Patent Document 4). However, this compound has been developed as a pigment added to the liquid crystal composition, and there is no description regarding basic physical properties as a liquid crystal material such as Δn. For this reason, as will be described later, the inventors of the present invention actually synthesized the analog of this compound and measured the physical properties. However, when used as a constituent component of the liquid crystal composition, the solubility and phase in other compounds (group) There was a difficulty in practical use in that it was poor in solubility. Moreover, although it is preferable to show a liquid crystal phase in a wide temperature range in order to use it as a structural component of a liquid crystal composition, it did not show sufficient properties in this respect.

JP-A-61-5031 JP-A-60-152427 JP-A-11-71338 JP-A-2-56456

  The problem to be solved by the present invention is to provide a material realizing high Δn, and also a liquid crystal composition comprising the compound as a constituent member, and a liquid crystal display device and a cholesteric liquid crystal display device using the liquid crystal composition Is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and found that the problems can be effectively solved by an acetylene compound into which an azobenzene moiety and a tetrahydronaphthalene structure are introduced, and have completed the present invention.

  The present invention provides a general formula (1)

Wherein R ¹ and R ² are each independently a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 1 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms, but R ¹ and R ² do not both represent a substituent selected from a fluorine atom, a chlorine atom and a cyano group. In addition, one or two or more hydrogen atoms in the alkoxy group and / or alkenyloxy group may be each independently substituted with a fluorine atom, and one or two or more —CH _{2 in} these groups may be substituted. -Each independently may be substituted with -O-, -CO-, -COO- or -OCO- so that two or more oxygen atoms are not continuously bonded, and one or non- 2 adjacent More -CH ₂ - may be substituted with -CH = CH- or -C≡C- independently,
Z ¹ , Z ² and Z ³ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, — CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group or 5,6,7,8-tetrahydronaphthalene-2,6-diyl group, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and Each hydrogen atom in A ⁶ may be independently substituted with a halogen atom, and one or two or more non-adjacent ones in A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ -CH = may be substituted with -N =, but A ² is a group represented by the general formula (2) or / and A ⁵ is a group represented by the general formula (3). ,

(In Formula (2) and Formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ each independently represent a hydrogen atom or a halogen atom. .)
m, n, and p each independently represent 0 or 1, but m + n + p represents 0-2. ), A liquid crystal composition containing the compound, a liquid crystal display device using the liquid crystal composition, a method for producing the compound represented by the general formula (1), and a raw material used in the production method in general Formula (4)

(In the formula, R ¹ is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or the number of carbon atoms. 2 to 12 alkenyloxy groups are represented, and one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkoxy group and / or alkenyloxy group may be each independently substituted with a fluorine atom. Furthermore, one or more of —CH ₂ — in these groups are each independently —O—, —CO—, —COO— or —OCO so that two or more oxygen atoms are not continuously bonded. One or non-adjacent two or more —CH ₂ — in these groups may be each independently substituted with —CH═CH— or —C≡C—. ,
Z ¹ is a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, —CH═CH—, —CF═CF—. _{, -CF 2 O -, - OCF} 2 -, - CF 2 CF 2 - or an -C≡C-, ^{a 1} is 1,4-phenylene group, a naphthalene-1,4-diyl group, naphthalene-2,6 6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 5,6,7,8-tetrahydronaphthalene-2,6-diyl group, and the hydrogen atom in A ¹ is Each may be independently substituted with a halogen atom, and one or more non-adjacent —CH═ in A ¹ may be replaced with —N═, and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom or halo Represents a gen atom, and m represents 0 or 1. The compound represented by this is provided.

  The compound represented by the general formula (1) provided by the present invention is stable against heat, light, etc., has excellent liquid crystallinity, and can be easily produced industrially. The obtained compound represented by the general formula (1) has a very large Δn and exhibits a wide liquid crystal phase temperature range. In addition, the compound represented by the general formula (1) has good solubility and compatibility with other liquid crystal materials, but is more soluble particularly when a part of the ring structure is halogenated with a fluorine atom or the like. The compatibility is good, and it can be suitably used as a constituent component of the liquid crystal composition.

  Therefore, when added to a liquid crystal material for a liquid crystal display element that requires a large Δn, problems such as precipitation do not occur and the characteristics can be improved, so it is very useful as a component of the liquid crystal material for a liquid crystal display element. In particular, it is very useful as a component of a liquid crystal material for a cholesteric liquid crystal display element that requires a large Δn.

In the general formula (1), R ¹ and R ² may be the same or different, but an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 1 carbon atom. It is preferable that it is a C12 alkoxy group, a C2-C12 alkenyloxy group, a fluorine atom, or a cyano group. In particular, to improve solubility, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, A fluorine atom or R ³ —Z ⁴ — (wherein R ³ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and one or more hydrogen atoms in the group) May be independently substituted with a fluorine atom, and Z ⁴ represents —CH═CH— or —C≡C—). In order to improve liquid crystallinity, the number of carbon atoms is 1-8. An alkyl group, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable. In order to increase the value of Δε, a fluorine atom or cyano Group is preferred, and in order to further increase Δn, R ¹ and at least one of at least one -CH ₂ in ^{R 2} - is preferably is substituted with -C = C-or ^-C≡C-, R 3 -C = C- and ^R 3 -C≡C -Is preferred, and R ³ -C≡C- is preferred. The alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be linear or branched, but are preferably linear. When branched, it may be substantially either the R or S form or the racemic form.

Z ¹ , Z ² and Z ³ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —CH═CH—, —CF ₂ O—, —OCF ₂ —. Alternatively, —C≡C— is preferable, and a single bond, —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, or —C≡C— is more preferable.

A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group or 5,6,7,8-tetrahydronaphthalene-2,6-diyl group, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and Each hydrogen atom in A ⁶ may be independently substituted with a halogen atom, and one or two or more non-adjacent ones in A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ -CH = may be substituted with -N =, but A ² is a group represented by the general formula (2), A ⁵ is a group represented by the general formula (3), or a group a ² is a group represented by the general formula (2) and that a ⁵ is represented by the general formula (3), a ² is the formula Is a group represented by 2) are preferred.

(In Formula (2) and Formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ each independently represent a hydrogen atom or a halogen atom. .). One or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ^{9 in} the general formula (2) or the general formula (3) is a halogen atom. It is more preferable that ^one or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ is a fluorine atom, and more preferably X ¹ , More preferably, two or more of X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are fluorine atoms, and two or more of X ⁵ , X ⁶ and X ⁷ are more preferably a fluorine atom, and particularly preferably X ⁵ and X ⁶ is a fluorine atom.

The other ring structures present are preferably each independently unsubstituted or a 1,4-phenylene group optionally substituted by one or more fluorine atoms, and A ² is represented by the general formula (2). A ¹ , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently an unsubstituted or 1,4-phenylene group optionally substituted by one or more fluorine atoms It is more preferable.

In order to improve the compatibility, it is preferable that the hydrogen atom on the carbon atom adjacent to the carbon to which —C≡C— of A ² and / or A ³ is bonded is substituted with a fluorine atom. A ² is a group represented by the general formula (2), X ⁵ and X ⁶ are fluorine atoms, and A ¹ , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently unsubstituted. Or a 1,4-phenylene group which is optionally substituted by one or more fluorine atoms. A ² is a group represented by the general formula (2), X ⁵ and X ⁶ are fluorine atoms, and A ¹ , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently unsubstituted. Or a 1,4-phenylene group which may be substituted by one or more fluorine atoms.

  Since Δn exhibits a large value when the number of aromatic rings is large, m, n, and p are preferably 1 in order to increase Δn. However, when the number of aromatic rings is large, the phase with other liquid crystal materials is large. Solubility will decrease. For this reason, m + n + p is 2 or less, but m + n + p is preferably 1, and m + n + p is more preferably 0.

Depending on the selection of R ^{1 to} R ² , A ^{1 to} A ⁶ , Z ^{1 to} Z ³ , m, n and p in the general formula (1), various types of compounds may be included. The compounds represented by the general formulas (1-1) to (1-36) are preferred.

(In the formula, R ^a and R ^b are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkenyloxy groups (one or two or more non-adjacent —CH ₂ — in R ^a and R ^b may each independently be substituted with —CH═CH— or —C≡C—). .)
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 composition is 1% by mass (hereinafter,% in the composition is mass). %).), Preferably 2% by mass or more, and more preferably 5% by mass or more. Moreover, since it will cause problems, such as precipitation, if there is much content, as an upper limit, it is preferable to contain 50 mass% or less, it is more preferable to contain 30 mass% or less, and it is further containing 20 mass% or less. The content is preferably 10% by mass or less.

  In order to adjust the physical properties of the liquid crystal composition, a compound having no liquid crystal phase can be added as needed in addition to the compound having a liquid crystal phase.

  Thus, as a preferable representative example of the nematic liquid crystal 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 formula is used as the first component. Although it contains at least one compound represented by (1), it is preferable to contain at least one of the following second to fourth components as other components.

  That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and one or more compounds selected from the compound group represented by the following general formulas (A1) to (A3) It is.

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 has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C. Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, a carbon atom A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and a terminal group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms Alkyl groups are preferred. 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 may be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or a fluorine atom By There naphthalene-2,6-diyl group or one to two fluorine atoms may be substituted 1,4-phenylene group 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 general formula (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. In addition, it is preferable that at least one of them in the general formula (A2) represents a single bond in the general formula (A3).

  Ring Z is an aromatic ring and can be represented by 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 the general formula (La), at least one of Y ^a and Y ^b is preferably a fluorine atom, and the general formula ( In Lb), at least one of Y ^{d to} Y ^f is preferably a fluorine atom, and more preferably Y ^d is a fluorine atom.

Terminal group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or 2 or more fluorine atoms optionally substituted carbon atoms 2 or 3 alkoxy groups, alkyl Represents a 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.

  Further, in the general formulas (A2) and (A3), the compound represented by the general formula (I) of the present invention is excluded.

  The third component is a so-called cyano p-type liquid crystal compound, and is one or more compounds selected from the group of 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 have a methyl or ethyl branch, and has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C. Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, a linear alkyl group having 1 to 7 carbon atoms, a carbon atom A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and a terminal group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms Alkyl groups are preferred. 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, a fluorine atom The good can have a naphthalene-2,6-diyl group or one to two fluorine atoms may be substituted 1,4-phenylene group is preferred. 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 general formula (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.

Ring Y is an aromatic ring and can be represented by the following general formulas (L ^d ) to (L ^f ).

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

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

  Further, in the general formulas (B2) and (B3), the compound represented by the general formula (I) of the present invention is excluded.

  The fourth component is a so-called n-type liquid crystal having a dielectric anisotropy of about 0, and one or more compounds selected from the compound group represented by the following general formulas (C1) to (C3) It is.

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 have a methyl or ethyl branch, and 3 to 6 Any —CH ₂ — present in the group may be —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═. Any hydrogen atom present in the group may be replaced by CF- or -C≡C-, and may be substituted by a fluorine atom or a trifluoromethoxy group. A linear alkyl 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 A linear alkyl group having 1 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms And 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. It is 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, one or two fluorine atoms, 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 A naphthalene-2,6-diyl group optionally substituted by a nitrogen atom, a tetrahydronaphthalene-2,6-diyl group optionally substituted by one or two fluorine atoms, and 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 may be within 1 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.

L ^g , L ^h and ^Li 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—, —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.

  In the general formulas (C2) and (C3), the compound represented by the general formula (I) of the present invention is excluded.

  More preferable forms in the general formula (C1) can be represented by the following general formulas (C1a) to (C1h).

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, or 4 to 7 carbon atoms. A linear 3-alkenyl group, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms, the terminal of which is substituted with an alkoxy group having 1 to 3 carbon atoms is represented. However, at least one represents 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. However, if the ring G1~ ring G3 is an aromatic ring, the corresponding ^{R f} is except 1-alkenyl group and alkoxy group, and when ring H1~ ring and H3 of the aromatic ring, the corresponding ^{R g} is 1-alkenyl and alkoxy Excluding groups.

  Ring G1 and Ring H1 are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, one or two fluorine atoms or a methyl group. 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, tetrahydronaphthalene-2 optionally substituted by 1 to 2 fluorine atoms, 6-diyl group, 1,4-cyclohexenylene group optionally substituted by 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, 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 atoms A more optionally substituted naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, and an optionally substituted 1 atom , 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, In this case, the other ring is a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group. Ring G2 and Ring H2 are each independently substituted with a trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group. 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, tetrahydronaphthalene-2 optionally substituted by 1 to 2 fluorine atoms, Represents a 6-diyl group, but in each compound, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, The number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by two fluorine atoms is preferably no more than one. The other ring is a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group. Ring G3 and Ring H3 are each independently a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group, and naphthalene-2 optionally substituted by one or more fluorine atoms , 6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 or 2 fluorine atoms, naphthalene optionally substituted by one or more fluorine atoms in each compound It is preferable that the number of the -2,6-diyl group and the tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 or 2 fluorine atoms is 1 or less.

  More preferable forms in the general formula (C2) can be represented by the following general formulas (C2a) to (C2m).

In the above formula, ring G1, ring G2, ring G3, ring H1, ring H2, and ring H3 have the same meanings as described above, ring I1 is the same as ring G1, ring I2 is the same as ring G2, and ring I3 is the same as ring G3. Represents meaning. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, and one or two fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted by 1, a 1,4-cyclohexenylene group optionally substituted by a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, The number of pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably 1 or less, and the other ring in that case is a trans-1,4-cyclohexylene group or 1 to 2 groups. A 1,4-phenylene group which may be substituted with a fluorine atom or a methyl group.
Next, the more preferable form in (C3) can be represented by the following general formulas (C3a) to (C3f).

  In the above formula, ring G1, ring G2, ring H1, ring H2, ring I1 and ring I2 have the same meanings as described above, and ring J1 has the same meaning as ring G1 or ring J2, respectively. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, and one or two fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted by 1, a 1,4-cyclohexenylene group optionally substituted by a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, The number of pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably 1 or less, and the other ring in that case is a trans-1,4-cyclohexylene group or 1 to 2 groups. A 1,4-phenylene group which may be substituted with a fluorine atom or a methyl group.

In the present invention, the compound of the general formula (1) can be produced, for example, as follows, but the spirit and scope of the present invention are not limited thereto.
(Manufacturing method 1) General formula (7)

(Wherein R ¹ , A ¹ , A ² , Z ¹ and m each independently represent the same meaning as in the general formula (1), X is a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, p A compound represented by -toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group) and trimethylsilylacetylene, tetrakistriphenylphosphine palladium (0), palladium (II) acetate or bis (trichloride) In the presence of a palladium-based transition metal catalyst such as phenylphosphine) palladium (II), a Sonogashira reaction is carried out in the presence of a base and a copper salt, thereby obtaining a compound represented by the general formula (8)

(Wherein R ¹ , A ¹ , A ² , Z ¹ and m each independently represent the same meaning as in general formula (1), and TMS represents a trimethylsilyl group) to obtain a compound represented by it can.

  Examples of the base include butylamine, diethylamine, triethylamine, diisopropylamine, piperidine, ammonia and the like, preferably triethylamine and diisopropylamine. Preferred examples of the copper salt include copper (I) iodide and copper (I) bromide. X can be exemplified by bromine, iodine and trifluoromethanesulfonyloxy groups, with iodine and trifluoromethanesulfonyloxy groups being particularly preferred.

  Any solvent can be used as long as it allows the reaction to proceed appropriately. Ether solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used, and amines used as bases can also be used. Can also be used as a solvent. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc. Benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. as group solvents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, water, etc. as polar solvents Can be cited as a good example. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and the like are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably 20 ° C to 90 ° C.

  Next, the compound represented by the general formula (8) is deprotected with acetylene using tetrabutylammonium fluoride or the like, and the general formula (9)

(Wherein, R ¹ , A ¹ , A ² , Z ¹ and m each independently represent the same meaning as in general formula (1)) can be obtained.

  Any solvent can be used as long as it allows the reaction to proceed appropriately, but ether solvents, hydrocarbon solvents, aromatic solvents, and the like can be preferably used. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc. Examples of the group solvent include benzene, toluene, xylene, mesitylene and the like. Of these, ether solvents such as 1,4-dioxane and tetrahydrofuran are preferred. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  Although reaction temperature can be performed in the recirculation | reflux temperature range from the freezing point of a solvent, -40 degreeC to 30 degreeC is preferable.

  Next, general formula (10)

(Wherein R ² , A ⁵ , A ⁶ , Z ³ and p independently represent the same meaning as in general formula (1)) and sodium nitrite were reacted under acidic conditions. After, general formula (11)

(Wherein A ³ , A ⁴ , Z ² and n each independently represent the same meaning as in general formula (1)) and a diazo coupling reaction under basic conditions with a compound represented by the general formula (12)

(Wherein R ² , A ^{3 to} A ⁶ , Z ² , Z ³ , n and p each independently represent the same meaning as in general formula (1)) can be obtained.

  As the acid used for the acidic condition, an inorganic acid is preferably used, and hydrochloric acid, sulfuric acid and the like are particularly preferable. As a base used for making it basic, an inorganic base is preferably used, and sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate are particularly preferable.

  Any solvent can be used as long as it allows the reaction to proceed suitably, but ether solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc., polar Examples of the solvent include methanol, ethanol, propanol, water and the like. Among these, water-soluble ether solvents such as 1,4-dioxane and tetrahydrofuran and water are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  Although reaction temperature can be performed in the recirculation | reflux temperature range from the freezing point of a solvent, -40 to 10 degreeC is preferable.

  Next, the compound represented by the general formula (12) is reacted with trifluoromethanesulfonic anhydride in the presence of a base, and the general formula (13)

(Wherein R ² , A ^{3 to} A ⁶ , Z ² , Z ³ , n and p each independently represent the same meaning as in general formula (1), and Tf represents a trifluoromethanesulfonyl group). Can be obtained.

  As the base, amines are preferably used, and triethylamine, diisopropylamine, and pyridine are particularly preferable.

  Any solvent may be used as long as it allows the reaction to proceed suitably. Ether solvents, hydrocarbon solvents, aromatic solvents, chlorine solvents, and the like can be preferably used. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc. Examples of the group solvent include benzene, toluene, xylene, mesitylene and the like, and examples of the chlorine solvent include dichloromethane, chloroform, 1,2-dichloroethane and the like. Of these, chlorinated solvents such as dichloromethane, chloroform, and 1,2-dichloroethane are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  Although reaction temperature can be performed in the recirculation | reflux temperature range from the freezing point of a solvent, -40 degreeC to 10 degreeC is preferable.

  Next, the compound represented by the general formula (13) and the compound represented by the general formula (9) are converted into tetrakistriphenylphosphine palladium (0), palladium (II) acetate or bis (triphenylphosphine) palladium dichloride. A compound represented by the general formula (1) can be obtained by performing a coupling reaction in the presence of a base and a copper salt in the presence of a palladium-based transition metal catalyst such as (II).

  Examples of preferred bases include butylamine, diethylamine, triethylamine, diisopropylamine, piperidine, and ammonia. Among them, triethylamine and diisopropylamine are preferred. Preferred examples of the copper salt include copper (I) iodide and copper (I) bromide.

  Any solvent can be used as long as it allows the reaction to proceed suitably. Ether solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used, and the amine used as the base can be selected. It can also be used as a solvent. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc. Benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. as group solvents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, water, etc. as polar solvents Can be cited as a good example. Of these, polar solvents such as tetrahydrofuran, N, N-dimethylformamide and N, N-dimethylacetamide are preferred. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably 20 ° C to 120 ° C.
(Manufacturing method 2) The compound represented by General formula (9) obtained by manufacturing method 1, and General formula (14)

(Wherein A ³ , A ⁴ , Z ² and n each independently represent the same meaning as in general formula (1), X is a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, p-toluenesulfonyl) An oxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group) and tetrakistriphenylphosphine palladium (0), palladium (II) acetate or bis (triphenylphosphine) palladium (II) chloride In the presence of a palladium-based transition metal catalyst such as a base and a copper salt in the presence of a Sonogashira reaction,

(Wherein R ¹ , A ^{1 to} A ⁴ , Z ¹ , Z ² , m and n each independently represent the same meaning as in general formula (1)) can be obtained.

  Examples of the base include butylamine, diethylamine, triethylamine, diisopropylamine, piperidine, and ammonia, preferably triethylamine, diisopropylamine, and ammonia. Preferred examples of the copper salt include copper (I) iodide and copper (I) bromide. Preferred examples of X include bromine, iodine and trifluoromethanesulfonyloxy groups, with iodine and trifluoromethanesulfonyloxy groups being more preferred.

  Any solvent can be used as long as it allows the reaction to proceed suitably. Ether solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used, and the amine used as the base can be selected. It can also be used as a solvent. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc. Benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. as group solvents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, water, etc. as polar solvents Can be cited as a good example. Of these, polar solvents such as tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and water are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably 20 ° C to 120 ° C.

  Next, after reacting the compound represented by the general formula (15) and sodium nitrite under acidic conditions, the general formula (16)

(Wherein A ⁵ , A ⁶ , Z ³ and p each independently represent the same meaning as in general formula (1)) and a diazo coupling reaction under basic conditions with a compound represented by the general formula (17)

(Wherein R ¹ , A ^{1 to} A ⁶ , Z ^{1 to} Z ³ , m, n, and p each independently represent the same meaning as in general formula (1)). it can.

  As the acid used for the acidic condition, an inorganic acid is preferably used, and hydrochloric acid, sulfuric acid and the like are particularly preferable. As the base used for basic conditions, an inorganic base is preferably used, and sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium hydrogen carbonate are particularly preferable.

  Any solvent can be used as long as it allows the reaction to proceed suitably, but ether solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc., polar Examples of the solvent include methanol, ethanol, propanol, water and the like. Among these, water-soluble ether solvents such as 1,4-dioxane and tetrahydrofuran and water are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  Although reaction temperature can be performed in the recirculation | reflux temperature range from the freezing point of a solvent, -40 degreeC to 10 degreeC is preferable.

  Next, the compound represented by the general formula (17) and the general formula (18)

(In the formula, R ⁴ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and X represents a chlorine atom, a bromine atom, an iodine atom, a benzenesulfonyloxy group, or p-toluenesulfonyloxy. Group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group) is reacted in the presence of a base to give a general formula (19)

(In the formula, R ¹ , A ^{1 to} A ⁶ , Z ^{1 to} Z ³ , m, n and p each independently represent the same meaning as in general formula (1), and R ⁴ has 1 to 12 carbon atoms. An alkyl group or an alkenyl group having 2 to 12 carbon atoms can be obtained.

  As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium carbonate and the like can be preferably used.

  Any solvent can be used as long as it allows the reaction to proceed suitably, but ether solvents, hydrocarbon solvents, polar solvents, and the like can be preferably used. Ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether, etc., and hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, etc., polar Preferred examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetone, acetonitrile and the like. Of these, ether solvents such as 1,4-dioxane and tetrahydrofuran and polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and acetone are preferable. Each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, but is preferably 20 ° C to 130 ° 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 “mass%”.

Various analyzes were performed by the following methods.
-Phase transition temperature: measured with a polarizing microscope equipped with a temperature control stage-Compound structure: confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS), etc. _TN-I represents the upper limit temperature indicating a nematic phase .

  The following abbreviations are used in compound descriptions.

THF: Tetrahydrofuran DMF: N, N-dimethylformamide TMS: Trimethylsilyl group Tf: Trifluoromethanesulfonyl group Et: Ethyl group Pr: n-propyl group Bu: n-butyl group Pen: n-pentyl group (Example 1) 4- Preparation of (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethylazobenzene

  25.0 g 2-propyl-6-iodo-1,2,3,4-tetrahydronaphthalene (obtained in the same manner as described in JP 2002-128717 A), 0.28 g copper iodide, 0.86 g Of tetrakis (triphenylphosphine) palladium (0) was mixed with 100 mL of DMF and 33 mL of triethylamine, heated to 70 ° C., 10.3 g of trimethylsilylacetylene was added dropwise, and the mixture was further stirred at 85 ° C. for 10 hours. After cooling, 150 mL of ice water was added, 10% hydrochloric acid was added, and after extraction with hexane, the organic phase was washed with 10% hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine in that order, followed by column chromatography and vacuum distillation. Purification gave 18.65 g of 2-propyl-6- (trimethylsilyl) ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene. Boiling point 153-154 ° C / 160-180Pa.

The resulting 18.65 g of 2-propyl-6- (trimethylsilyl) ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene is dissolved in 70 mL of THF and kept at 7-16 ° C. here. 64 mL of tetrabutylammonium fluoride 1.0M THF solution was added dropwise to the solution, and the mixture was further stirred at room temperature for 1 hour. The mixture was acidified with 10% hydrochloric acid while cooling with ice, extracted with hexane, washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, saturated aqueous ammonium chloride, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purification by column chromatography (solvent: hexane) gave 14.1 g of 2-propyl-6-ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene.
The resulting 14.1 g of 2-propyl-6-ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene was dissolved in 100 mL of DMF, and 21.8 g of trifluoromethanesulfonic acid 4′-ethylazobenzene-4 -Yl (obtained using 4-ethyl-4'-hydroxyazobenzene (obtained in the same manner as described in Chemical Communication, 2010, 46, 2587-2589)), 0.23 g of copper (I) iodide 0.70 g of tetrakis (triphenylphosphine) palladium (0) was added dropwise at 70 ° C. to a mixture of 100 mL of DMF and 33 mL of triethylamine, and further stirred at 80 ° C. for 4 hours. Under ice-cooling, ice water was added, followed by filtration. The resulting precipitate was dissolved in toluene and purified by column chromatography (solvent: toluene). Further, recrystallization from acetone-toluene gave 18.8 g of 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4′-ethylazobenzene. It was.

MS m / z: 442 [M +]
Phase transition temperature (° C.): Cr 114 N 277 (decomposition)
Similarly, the following compounds were obtained.
4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propylazobenzene
4- (2-Pentyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethylazobenzene 4- (2-pentyl-5,7-difluoro-1, 2,3,4-Tetrahydronaphthalen-6-yl) ethynyl-4'-propylazobenzene (Example 2) 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene-6 -Ill) Ethynyl-4'-ethoxyazobenzene production

  In a suspension of 18.7 g 4-iodoaniline, 0.3 g copper iodide, 0.6 g bis (triphenylphosphine) palladium (II) dichloride, 160 mL 1 M aqueous ammonia, 180 mL THF, 20 g 2-propyl -6-Ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene (obtained in the same manner as in Example 1) was dissolved in 20 mL of THF and added dropwise at 40 ° C., and the mixture was further stirred for 4 hours. Saturated saline was added, and the organic layer was separated. The aqueous layer was extracted with THF, the organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purified by column chromatography, then dissolved in THF, 6M hydrochloric acid was added, the organic layer was separated, washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 25.6 g of 4 -(2-Propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynylaniline hydrochloride was obtained.

  The resulting 25.6 g of 4- (6-propyl-1,3-difluoronaphthalen-2-yl) ethynylaniline hydrochloride, 10 mL of concentrated hydrochloric acid and 260 mL of THF were mixed, and 5.9 g of sodium nitrite was mixed there. Was dissolved in 30 mL of water and added dropwise under ice cooling, and the mixture was further stirred for 1 hour to prepare a diazonium salt solution. 8.0 g of phenol, 8.1 g of sodium carbonate and 3.4 g of sodium hydroxide were dissolved in 120 mL of water, and the prepared diazonium solution was added dropwise under ice cooling, followed by further stirring for 3 hours. 50 mL of 15% hydrochloric acid was added, followed by extraction with THF. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purification by column chromatography and recrystallization gave 18.3 g of 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-hydroxyazobenzene. It was.

  18.3 g of 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4′-hydroxyazobenzene, 10.0 g of iodoethane, 15.0 g of Potassium carbonate was mixed with 70 mL of DMF and stirred at 75 ° C. for 12 hours. The mixture was cooled to room temperature, poured into 140 mL of ice water, and the precipitate collected by filtration was dissolved in a toluene-THF mixed solvent, washed with saturated brine, and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Purification by column chromatography and recrystallization gave 11.2 g of 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethoxyazobenzene. It was.

MS m / z: 458 [M +]
Similarly, the following compounds were obtained.
4- (2-Propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propoxyazobenzene
4- (2-Pentyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propoxyazobenzene
4- (2-pentyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethoxyazobenzene (Example 3) 4- (2-propyl-1,2 , 3,4-Tetrahydronaphthalen-6-yl) ethynyl-4'-ethylazobenzene

  30 g of 2-propyl-1,2,3,4-tetrahydro-2-naphthol (obtained in the same manner as described in JP-A-2001-19648), 20 g of pyridine were dissolved in 150 mL of dichloromethane, 49.0 g of trifluoromethanesulfonic anhydride was added dropwise thereto under ice cooling. The mixture was further stirred at room temperature for 5 hours, and 10% hydrochloric acid was added dropwise under ice-cooling until acidic. The organic layer was separated, washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Purification by column chromatography gave 49.4 g of 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl trifluoromethanesulfonate.

  Using the obtained 49.4 g of 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl trifluoromethanesulfonate, in the same manner as in Example 1, 2-propyl-6-ethynyl-1, After derivatization to 2,3,4-tetrahydronaphthalene, 4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4′-ethylazobenzene was obtained.

MS m / z: 406 [M +]
Similarly, the following compounds were obtained.
4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propylazobenzene
4- (2-Ethyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propylazobenzene
4- (2-Ethyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethylazobenzene (Example 4) 4- (2-propyl-1,2,3,4-tetrahydro Naphthalen-6-yl) ethynyl-4'-ethoxyazobenzene

  4- (2-propyl-1,2,3,4) was obtained in the same manner as in Example 2 except that 2-propyl-6-ethynyl-1,2,3,4-tetrahydronaphthalene obtained in Example 3 was used. -Tetrahydronaphthalen-6-yl) ethynyl-4'-ethoxyazobenzene was obtained.

MS m / z: 422 [M +]
Similarly, the following compounds were obtained.
4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propoxyazobenzene
4- (2-Ethyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-propoxyazobenzene
4- (2-Ethyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4′-ethoxyazobenzene (Example 5) (4- (4-propylphenyl) ethynylphenyl) (2-propyl -1,2,3,4-Tetrahydronaphthalen-6-yl) diazene

  25.0 g of (2-propyl-1,2,3,4-tetrahydronaphthalene-6-amine (2-propyl-1,2,3,4-tetrahydronaphthalene is nitrated and then hydrogenated using Pd / C The nitro group could be reduced by mixing.) 17 mL of concentrated hydrochloric acid and 400 mL of THF were mixed, and 10.0 g of sodium nitrite was dissolved in 50 mL of water, added dropwise under ice cooling, and further stirred for 1 hour. The diazonium salt solution was prepared by dissolving 13.5 g of phenol, 4.8 g of sodium carbonate, and 5.7 g of sodium hydroxide in 200 mL of water, and the prepared diazonium solution was added dropwise under ice-cooling for another 3 hours. 85 mL of 15% hydrochloric acid was added, and the mixture was extracted with THF.The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Dissolve 20 g of pyridine in 150 mL of dichloromethane and add 50.0 g of trifluoromethanesulfonic acid. The mixture was added dropwise under ice-cooling, further stirred at room temperature for 5 hours, and 10% hydrochloric acid was added dropwise under ice-cooling until it became acidic, and the organic layer was separated and washed with saturated aqueous sodium bicarbonate and saturated brine in this order. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and purified by column chromatography to obtain 27.4 g of trifluoromethanesulfonic acid 4- (2-propyl-1,2,3,4-tetrahydronaphthalene-6 -Yl) diazenylphenyl was obtained.

  Trifluoromethanesulfonic acid 4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) diazenylphenyl and 2-propyl-6-ethynylbenzene in the same manner (4- (4- Propylphenyl) ethynylphenyl) (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) diazene was obtained.

MS m / z: 420 [M +]
Comparative Example 1 Production of 4- (4-pentylphenyl) ethynyl-4′-propoxyazobenzene

Similar to Example 2 except that 4-pentyl-1-ethynylbenzene was used instead of 2-propyl-6-ethynyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalene and iodopropyl was used instead of iodoethane. In this way, 4- (4-pentylphenyl) ethynyl-4′-propoxyazobenzene was obtained.
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 _N-I ): 77.9 ° C.
Refractive index anisotropy (Δn): 0.1024
90% of the base liquid crystal (H) and 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'- obtained in Example 1 A liquid crystal composition composed of 10% ethylazobenzene was prepared.
(Example 7) Preparation of liquid crystal composition-2
90% of base liquid crystal (H) and 4- (2-propyl-5,7-difluoro-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethoxy obtained in Example 2 A liquid crystal composition composed of 10% azobenzene was prepared.
Example 8 Preparation of Liquid Crystal Composition-3
Liquid crystal comprising 90% of the base liquid crystal (H) and 10% of 4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethylazobenzene obtained in Example 3 A composition was prepared.
Example 9 Preparation of Liquid Crystal Composition-4
A liquid crystal comprising 90% of the base liquid crystal (H) and 10% of 4- (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) ethynyl-4'-ethoxyazobenzene obtained in Example 4 A composition was prepared.
Example 10 Preparation of Liquid Crystal Composition-5
90% of base liquid crystal (H) and (4- (4-propylphenyl) ethynylphenyl) (2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl) diazene obtained in Example 5 10 % Liquid crystal composition was prepared.
Comparative Example 2 Preparation of Liquid Crystal Composition-6
A liquid crystal composition comprising 90% of the base liquid crystal (H) and 10% of 4- (4-pentylphenylethynyl) -4′-propoxyazobenzene obtained in Comparative Example 1 was prepared.

The following table shows Δn of the liquid crystal compositions prepared in Examples 6 to 10 and Comparative Example 2 together with the base liquid crystal (H), and Δn of the compounds of Examples 1 to 5 and Comparative Example 1 obtained by extrapolation therefrom. Shown in In addition, _TN-I of each liquid crystal composition is shown in the same table.

  As mentioned above, this invention compound represented by General formula (1) is very large compared with the compound of the said patent documents 1, 2 and 3 similarly to the compound of the comparative example 1 which is a compound of the said patent document 4. It can be seen that Δn is shown.

However, when the liquid crystal compositions of Examples 6 to 10 and Comparative Example 2 were allowed to stand at room temperature for one week, the composition of Comparative Example 2 showed crystal precipitation, whereas the liquid crystals of Examples 6 to 10 were observed. The composition had no precipitation and maintained a stable liquid crystal phase. Furthermore, it can be seen that the liquid crystal compositions of Examples 6 to 10 have a high _TN-I compared with Comparative Example 2 and exhibit a liquid crystal phase in a wide temperature range. From these results, it can be seen that the compound of the present invention exhibits a large Δn and has both good compatibility and excellent liquid crystallinity.

  Moreover, it turned out that the cholesteric liquid crystal display element produced using the liquid crystal composition of Examples 6-10 shows the outstanding display characteristic.

Claims (18)

General formula (1)

Wherein R ¹ and R ² are each independently a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 1 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms, but R ¹ and R ² do not both represent a substituent selected from a fluorine atom, a chlorine atom and a cyano group. In addition, one or two or more hydrogen atoms in the alkoxy group and / or alkenyloxy group may be each independently substituted with a fluorine atom, and one or two or more —CH _{2 in} these groups may be substituted. -Each independently may be substituted with -O-, -CO-, -COO- or -OCO- so that two or more oxygen atoms are not continuously bonded, and one or non- 2 adjacent More -CH ₂ - may be substituted with -CH = CH- or -C≡C- independently,
Z ¹ , Z ² and Z ³ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, — CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group or 5,6,7,8-tetrahydronaphthalene-2,6-diyl group, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and Each hydrogen atom in A ⁶ may be independently substituted with a halogen atom, and one or two or more non-adjacent ones in A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ -CH = may be substituted with -N =, but A ² is a group represented by the general formula (2) or / and A ⁵ is a group represented by the general formula (3). ,

(In Formula (2) and Formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ each independently represent a hydrogen atom or a halogen atom. .)
m, n, and p each independently represent 0 or 1, but m + n + p represents 0-2. ) A compound represented by The general formula (1), wherein one or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are halogen atoms. Compound. The general formula (1), wherein one or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are fluorine atoms. Compound. The compound according to claim 1, wherein in the general formula (1), X ⁵ and X ⁶ are fluorine atoms. In General Formula (1), R ¹ and R ² are each independently R ³ —Z ⁴ — (wherein R ³ represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms. And one or more hydrogen atoms in the group may be independently substituted with fluorine atoms, and Z ⁴ represents —CH═CH— or —C≡C—. The compound of any one of 1-4. In the general formula (1) A compound according to claim 1 is a group A ² is represented by the general formula (2). In General formula (1), m, n, and p are 0, The compound of any one of Claims 1-6. In General Formula (1), at least one of R ¹ and R ² is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 2 carbon atoms. The alkenyloxy group of -12 or R < ³ > -Z < ⁴ >-, The compound of any one of Claims 5-7. In General Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and the number of carbon atoms. It is a 2-12 alkenyloxy group or R < ³ > -Z < ⁴ >-, The compound of any one of Claims 5-7. In the general formula (1), compound according to any one of claims 1-8 either of R ¹ or R ² is a fluorine atom or a cyano group. A liquid crystal composition comprising one or more compounds represented by the general formula (1) according to any one of claims 1 to 10. A liquid crystal display device using the liquid crystal composition according to claim 11. A cholesteric liquid crystal display element using the liquid crystal composition according to claim 11. General formula (4)

(In the formula, R ¹ is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or the number of carbon atoms. 2 to 12 alkenyloxy groups are represented, and one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkoxy group and / or alkenyloxy group may be each independently substituted with a fluorine atom. Furthermore, one or more of —CH ₂ — in these groups are each independently —O—, —CO—, —COO— or —OCO so that two or more oxygen atoms are not continuously bonded. One or non-adjacent two or more —CH ₂ — in these groups may be each independently substituted with —CH═CH— or —C≡C—. ,
Z ¹ is a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —C ₄ H ₈ —, —COO—, —OCO—, —CH═CH—, —CF═CF—. _{, -CF 2 O -, - OCF} 2 -, - CF 2 CF 2 - or an -C≡C-, ^{a 1} is 1,4-phenylene group, a naphthalene-1,4-diyl group, naphthalene-2,6 6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 5,6,7,8-tetrahydronaphthalene-2,6-diyl group, and the hydrogen atom in A ¹ is Each may be independently substituted with a halogen atom, and one or more non-adjacent —CH═ in A ¹ may be replaced with —N═, and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a hydrogen atom or halo Represents a gen atom, and m represents 0 or 1. ) A compound represented by The compound according to claim 14, wherein, in the general formula (4), two or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are halogen atoms. The compound according to claim 14, wherein, in the general formula (4), two or more of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are fluorine atoms. The compound according to claim 14, wherein, in the general formula (4), X ⁵ and X ⁶ are fluorine atoms. A compound represented by the general formula (4) according to any one of claims 14 to 17, wherein the compound represented by the general formula (1) according to any one of claims 1 to 10 is used. A method for producing the represented compound.