JP2011207871A - Liquid crystal compound, method for producing the same, liquid crystal composition and liquid crystal electrooptical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal compound that exhibits excellent compatibility with another liquid crystal material or a non-liquid crystal material and is chemically stable, a method for producing the same, a liquid crystal composition comprising the compound, and a liquid crystal display.SOLUTION: The liquid crystal compound is represented by formula (1) and has a linking group having a -CH=CFCFO- structure, R-(A)-Z-(A)-Z-(A)-Z-A-CH=CFCFO-A-Z-(A)-Z-(A)-R(1), where Ato Aare each independently a trans-1,4-cyclohexylene group, 1,3-cyclobutylene group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,4-phenylene group.

Description

  The present invention relates to a liquid crystal compound, a method for producing the same, a liquid crystal composition containing the compound, and a liquid crystal display device.

Liquid crystal elements include mobile devices such as mobile phones and PDAs, display devices for office automation equipment such as copiers and personal computer monitors, display devices for home appliances such as liquid crystal televisions, clocks, calculators, measuring instruments, automotive meters, It is used for applications such as cameras, and various performances such as a wide operating temperature range, a low operating voltage, high-speed response, and chemical stability are required.
In such a liquid crystal element, a material exhibiting a liquid crystal phase is used, but at present, not all of these characteristics are satisfied by a single compound, and a plurality of excellent one or more characteristics are provided. Liquid crystal compounds and non-liquid crystal compounds are mixed to satisfy the required performance as a liquid crystal composition.
Among various properties required for compounds used in liquid crystal compositions in the field of liquid crystal elements, the liquid crystal elements have excellent compatibility with other liquid crystal materials or non-liquid crystal materials, are chemically stable, and are liquid crystal elements. It is an important problem to provide a compound or a liquid crystal composition having a property of being excellent in high-speed response in a wide temperature range and being capable of being driven at a low voltage.

As a solution to such problems, there have been unsaturated linking group-containing compounds substituted with fluorine atoms such as -CF = CF- and -CH = CF-, and -CF ₂ O-linking group-containing compounds. It has been used. (Patent Document 1, Patent Document 2, Patent Document 3)
However, the unsaturated linking group-containing compound has a problem that it lacks stability to light. Further, the —CF ₂ O— linking group-containing compound has a problem that —CF ₂ O— may be decomposed depending on the structure.

Japanese Patent Laid-Open No. 03-041037 JP 05-70382 A Japanese Patent Laid-Open No. 05-112778

An object of the present invention is to provide a liquid crystal compound that is excellent in compatibility with other liquid crystal materials or non-liquid crystal materials and is chemically stable, and a method for producing the same. Another object of the present invention is to provide a liquid crystal compound having a large dielectric anisotropy and the like in addition to the above characteristics by adjusting each group in the liquid crystal compound.
In addition, the present invention provides a liquid crystal composition suitable for obtaining a liquid crystal electro-optical element containing the liquid crystal compound and capable of being driven at a low voltage in a wide temperature range and having a high display quality, and a liquid crystal electrolysis using the liquid crystal composition. An object is to provide an optical element.

As a result of intensive investigations, the present inventors have found that when a compound having a specific structure having a —CH═CFCF ₂ O— linking group is contained in the liquid crystal composition, the liquid crystal composition thereof is solved as a solution to such a problem. We have found that liquid crystal electro-optic elements using materials are useful compounds that satisfy various performance requirements such as a wide operating temperature range, low operating voltage, high-speed response, and chemical stability. It was. That is, this invention provides the liquid crystal compound represented by Formula (1).
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH = CFCF 2 O-A 5 -Z 4 - (A 6) d _{^{-Z 5 - (A 7) e}} -R 2 (1)
The symbol in Formula (1) shows the following meanings.
R ¹ and R ^{2 are} each independently a hydrogen atom, a halogen atom, —CN, —NCS, —SF ₅ or a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and one of the groups The above —CH ₂ — may be substituted with an etheric oxygen atom (—O—) or a thioetheric sulfur atom (—S—), and any hydrogen atom in the group is substituted with a fluorine atom. Also good.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ : independently of each other, trans-1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1, 3 -Cyclobutylene group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group Or 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. Two —CH ₂ — groups may be substituted with —O— or —S—.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ : each independently a single bond, a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and one or more —CH in the group ₂ — may be substituted with —O— or —S—, and any hydrogen in the group may be substituted with fluorine.
a, b, c, d, e: 0 or 1 independently of each other. However, 0 ≦ a + b + c + d + e ≦ 3.

Among the liquid crystal compounds represented by the formula (1), compounds represented by the following formula (1-1) are preferable.
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH = CFCF 2 O-A 51 -Z 41 - (A 61) d _{^{-Z 51 - (A 71) e}} -R 21 (1-1)
The symbols in the formula have the following meanings.
R ¹¹ and R ^{21 are} each independently a hydrogen atom, a fluorine atom, —SF ₅ , an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O— or —S—, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ : Independently of each other, a trans-1,4-cyclohexylene group or a 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. One —CH ₂ — group may be substituted with —O— or —S—.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ^{51 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and one or more —CH ₂ — in the group is —O—. In addition, one or more hydrogen atoms in the group may be substituted with a fluorine atom.
a, b, c, d and e have the same meaning as described above.

Among the liquid crystal compounds represented by the formula (1), a compound represented by the following formula (1-2) is more preferable.
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH = CFCF 2 O-A 52 -Z 42 - (A 62) d _{^{-Z 52 - (A 72) e}} -R 22 (1-2)
The symbols in the formula have the following meanings.
R ¹² : a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O—, and one or more hydrogen atoms in the group may be substituted with fluorine.
R ²² : a hydrogen atom, a fluorine atom, —SF ₅ , or an alkyl group having 1 to 10 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O—, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
A ¹² , A ²² , A ³² , A ⁴² , A ⁵² , A ⁶² , A ⁷² : independently of each other, trans-1,4-cyclohexylene group, 1,4-phenylene group, or one or two of them 1,4-phenylene group substituted by a fluorine atom.
Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² : each independently a single bond, an alkylene group having 1 to 4 carbon atoms.
a, b, c, d and e have the same meaning as described above.

Moreover, it is preferable that the manufacturing method of the liquid crystal compound represented by said Formula (1) includes the following process (1) and the following process (2).
Step (1): A step of halogenating a compound represented by the following formula (2) to obtain a compound represented by the following formula (3).
R ^1- (A ¹ ) _a -Z ^1- (A ² ) _b -Z ^2- (A ³ ) _c -Z ³ -A ⁴ -CH ₂ CF = CF ₂ (2)
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH 2 CFX 1 CF 2 X 2 (3)
Step (2): A step of obtaining a liquid crystal compound represented by the formula (1) by reacting a compound represented by the following formula (4) with the compound represented by the formula (3).
Y ¹ O—A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e —R ² (4)
R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , Z ¹ , Z ² , Z in Formula (2), Formula (3) and Formula (4) ³ , Z ⁴ , Z ⁵ , a, b, c, d and e have the same meaning as described above. X ¹ and X ² are halogen atoms, and Y ¹ is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.

  The present invention also provides a compound represented by the formula (3).

  The present invention also provides a liquid crystal composition comprising the liquid crystal compound (1) represented by the formula (1).

  The present invention also provides a liquid crystal electro-optical element formed by sealing the liquid crystal composition between two substrates provided with electrodes.

The liquid crystal compound represented by the formula (1) of the present invention is excellent in compatibility with other liquid crystal materials or non-liquid crystal materials, and is chemically stable. In addition, the compound of the present invention has various performances required for a liquid crystal element, specifically, for example, a wide operating temperature range, by appropriately selecting a ring group, a substituent and a linking group constituting the compound. A liquid crystal composition satisfying low operating voltage, high-speed response, chemical stability, etc. can be prepared. In addition, when the liquid crystal composition is used in a liquid crystal electro-optical element, it can be driven at a low voltage with excellent high-speed response in a wide temperature range.
According to the production method of the present invention, a compound having a —CH═CFCF ₂ O— linking group is highly versatile and can be easily and efficiently produced easily and efficiently industrially.

The present invention will be described in more detail below.
In this specification, the liquid crystal compound represented by the formula (1) is referred to as a compound (1), and the compounds represented by other formulas are also described in the same manner.

In the compound (1) of the present invention, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, —CN, —NCS, —SF ₅ or a monovalent aliphatic carbon atom having 1 to 18 carbon atoms. A hydrogen group, and one or more —CH ₂ — in the group may be substituted with —O— or —S—, and any hydrogen atom in the group may be substituted with a fluorine atom. In addition, both of these groups and hydrogen atom substitution may be included.
Hereinafter, an alkyl group including substitution with at least one of —O—, —S— and a fluorine atom is referred to as a “substituted alkyl group”.
An alkenyl group containing a substitution with at least one of —O—, —S— and a fluorine atom is referred to as a “substituted alkenyl group”.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, and among them, an alkyl group or an alkenyl group is preferable.
Examples of the substituted alkyl group include an alkoxy group, an alkoxyalkyl group, an alkylthio group, an alkylthioalkyl group, a fluoroalkyl group, and a fluoroalkoxy group.
Examples of the substituted alkenyl group include an alkenyloxy group, an alkenyloxyalkyl group, an alkenylthio group, an alkenylthioalkyl group, a fluoroalkenyl group, and a fluoroalkenyloxy group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a heptyloxy group, and an octyloxy group.
Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, and a propoxypropyl group.
Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
Examples of alkylthioalkyl groups include methylthiomethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, methylthioethyl, ethylthioethyl, propylthioethyl, methylthiopropyl, ethylthiopropyl, propylthio A propyl group etc. are mentioned.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 3-butenyl group, and 3-pentenyl group.
Examples of the alkenyloxy group include an allyloxy group.
Fluoroalkyl groups include trifluoromethyl, fluoromethyl, 2-fluoroethyl, difluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2 -Fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 5-fluoropentyl group and the like can be mentioned.
Fluoroalkoxy groups include fluoromethoxy group, trifluoromethoxy group, difluoromethoxy group, pentafluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, heptafluoropropoxy group, 1,1,2,3, Examples include 3,3-hexafluoropropoxy group.
Examples of the fluoroalkoxyalkyl group include a trifluoromethoxymethyl group.
As the fluoroalkenyl group, 2-fluoroethenyl group, 2,2-difluoroethenyl group, 1,2,2-trifluoroethenyl group, 3-fluoro-1-butenyl group, 4-fluoro-1-butenyl group Etc.
Examples of the fluoroalkylthio group include a trifluoromethylthio group, a difluoromethylthio group, a 1,1,2,2-tetrafluoroethylthio group, a 2,2,2-trifluoroethylthio group, and the like.

R ¹ and R ² are hydrogen atom, halogen atom, —CN, —NCS, —SF ₅ , alkyl group, alkenyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, alkenyl group, alkenyloxy group. An alkenylthio group, a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkoxyalkyl group, a fluoroalkenyl group, and a fluoroalkylthio group are preferred.

Among these, as R ¹ and R ² , since reactivity and side reaction are unlikely to occur, a hydrogen atom, a fluorine atom, —SF ₅ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A substituted alkyl group having 1 to 18 carbon atoms and a substituted alkenyl group having 2 to 18 carbon atoms are preferable.

In particular, R ¹ is particularly preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 1 to 10 carbon atoms.
R ² is particularly preferably a fluorine atom, —SF ₅ , a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 1 to 10 carbon atoms.

In the compound (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ and A ⁷ are independently of each other a trans-1,4-cyclohexylene group, 1,3-cyclohexane. Butylene group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,4-phenylene group.
One or more hydrogen atoms in each of these groups A ^{1 to} A ⁷ may be substituted with a halogen atom, and one or two of the ═CH— groups constituting each ring of A ^{1 to} A ⁷ are It may be substituted with a nitrogen atom, and one or two —CH ₂ — groups may be substituted with —O— or —S—, and may contain any of these groups and hydrogen atoms. Good. For a group containing such a substitution, the term “substituted” is added to the front of each ring group name, for example, “substituted 1,4-phenylene group”, “substituted trans-1,4-cyclohexylene group”, etc. May be called. The halogen atom here is preferably a chlorine atom or a fluorine atom.

In the case where A ^{1 to} A ⁷ are 1,4-phenylene groups and further have a halogen atom as a substituent, the number of halogen atoms substituted on one 1,4-phenylene group is 1 to 4, Of these, one or two are preferred. When it is a trans-1,4-cyclohexylene group and further has a halogen atom as a substituent, the number of halogen atoms to be substituted is preferably 1 to 4. The halogen atom may be bonded to the 1st or 4th carbon atom of the cyclohexylene group.
Examples of the 1,4-phenylene group substituted with a nitrogen atom include 2,5-pyrimidinylene group and 2,5-pyridinylene group.
Examples of the substituted trans-1,4-cyclohexylene group by —O— or —S— include 1,3-dioxane-2,5-diyl group and 1,3-dithian-2,5-diyl group. It is done.

As A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ and A ⁷ , trans-1,4-cyclohexylene group, 1,4-phenylene group, A substituted trans-1,4-cyclohexylene group and a substituted 1,4-phenylene group are preferred.
Among these, a trans-1,4-cyclohexylene group, a 1,4-phenylene group, and a 1,4-phenylene group substituted with one or two fluorine atoms are particularly preferable.

In the compound (1), Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a single bond, a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, One or more —CH ₂ — in the group may be substituted with —O— or —S—, and one or more hydrogen atoms in the group may be substituted with a fluorine atom. Any substitution of hydrogen atoms may be included. A group having such substitution may be referred to with the word “substitution”.
The substituted alkylene _{group, -CF 2 CF 2 -, -} CF 2 CH 2 -, - CH 2 CF 2 -, - CHFCH 2 -, - CH 2 CHF -, - CF 2 CHF -, - CHFCF 2 -, - CH ₂ O—, —OCH ₂ —, —CH ₂ S—, —SCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ O— _{, -C 2 H 4 CF 2 O-} , and the like.
Further, when Z ¹ , Z ² , Z ³ , Z ⁴ or Z ⁵ is a single bond, it means that groups existing on both sides of each group are directly bonded. For example, when Z ¹ is a single bond and a and b are 1, A ¹ and A ² are directly bonded. When Z ¹ , Z ² and Z ³ are single bonds and a, b and c are 0, R ¹ and A ⁴ are directly bonded.

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each a single bond, an alkylene group having 1 to 4 carbon atoms, a fluorine-substituted alkylene group corresponding to the group, or —O— for ease of synthesis or the like. A substituted alkylene group is preferred.
Among these, a single bond and an alkylene group having 1 to 4 carbon atoms are particularly preferable.

In the compound (1) of the present invention, a, b, c, d and e are 0 or 1 independently of each other.
However, 0 ≦ a + b + c + d + e ≦ 3.
a, b, c, d and e can be appropriately selected according to the properties required of the compound.
For example, when importance is attached to the fact that the compound (1) has low viscosity or the compound is excellent in compatibility with other liquid crystal materials or non-liquid crystal materials, 0 ≦ a + b + c + d + e ≦ 1 is preferable. On the other hand, when emphasizing the high liquid crystal temperature range of the compound, it is preferable that 1 ≦ a + b + c + d + e ≦ 3.

From the viewpoint of increasing Δε of the compound (1), “—A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e which is an O-side linking group of —CH═CFCF ₂ O—. It is considered that —R ² ”is preferably an electron withdrawing group. The electron withdrawing property of “−A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e —R ² ” means that in compound (1), d = e = 0, Z ⁴ and It is more electron withdrawing than “—A ⁵ —R ² ” in which Z ⁵ is a single bond and R ² is a hydrogen atom and A ⁵ is an unsubstituted phenylene group or cyclohexylene group. means.

In the case where “—A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e —R ² ” is an electron withdrawing group, it is mentioned that each group is as follows. It is done.

R ² : fluorine atom, —OCF ₃ , —OCF ₂ H, —CN, —NCS, or —SF ₅
A ⁵ , A ⁶ , A ⁷ : independently of each other, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, or a 2,6-difluoro-1,4-phenylene group.
Z ⁴ , Z ⁵ : single bond d, e: 0 or 1 independently of each other
The substitution positions of the substituted ring groups in A ⁵ , A ⁶ and A ⁷ are the 4th position closer to R ¹ and the 1st position closer to R ² .

In a conventionally known —CF ₂ O— linking group-containing compound, when a 1,4-phenylene group is substituted on the carbon atom side of —CF ₂ O—, if the group is not substituted with a fluorine atom, The CF ₂ O— linking group is unstable and may be converted to —COO— by hydrolysis.
Furthermore, in an unsaturated linking group-containing compound such as —CF═CF—, when a 1,4-phenylene group is substituted on the linking group, cis-trans isomerization occurs due to ultraviolet light or visible light. There is a problem that it is easy.
In contrast, in the compound having the —CH═CFCF ₂ O— linking group of the present invention, the linking group may be substituted with a 1,4-phenylene group not substituted with a fluorine atom. The decomposition and isomerization hardly occur and the stability of the compound is remarkably improved.
Therefore, the compound having a —CH═CFCF ₂ O— linking group of the present invention is stable even if the structure of the ring group at both ends of the linking group is not limited to a fluorine-substituted 1,4-phenylene group or the like. It is expected to have a feature that can be obtained.

As the compound (1) of the present invention, the compound (1-1) is preferable.
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH = CFCF 2 O-A 51 -Z 41 - (A 61) d _{^{-Z 51 - (A 71) e}} -R 21 (1-1)
The symbols in the formula have the following meanings.
R ¹¹ and R ^{21 are} each independently a hydrogen atom, a fluorine atom, —SF ₅ , an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O— or —S—, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ : Independently of each other, a trans-1,4-cyclohexylene group or a 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. One —CH ₂ — group may be substituted with —O— or —S—.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ^{51 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and one or more —CH ₂ — in the group is —O—. In addition, one or more hydrogen atoms in the group may be substituted with a fluorine atom.
a, b, c, d and e have the same meaning as described above.

As the compound (1) of the present invention, the compound (1-2) is more preferable.
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH = CFCF 2 O-A 52 -Z 42 - (A 62) d _{^{-Z 52 - (A 72) e}} -R 22 (1-2)
The symbols in the formula have the following meanings.
R ¹² : a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O—, and one or more hydrogen atoms in the group may be substituted with fluorine.
R ²² : a hydrogen atom, a fluorine atom, —SF ₅ , or an alkyl group having 1 to 10 carbon atoms. One or more —CH ₂ — in the group may be substituted with —O—, and one or more hydrogen atoms in the group may be substituted with fluorine.
A ¹² , A ²² , A ³² , A ⁴² , A ⁵² , A ⁶² , A ⁷² : independently of each other, trans-1,4-cyclohexylene group, 1,4-phenylene group, one or two 1,4-phenylene group substituted by a fluorine atom.
Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² : each independently a single bond, an alkylene group having 1 to 4 carbon atoms.
a, b, c, d and e have the same meaning as described above.

The production method of the compound (1) of the present invention includes the step (1) of obtaining a compound (3) as an intermediate by adding a halogen atom to the compound (2), and the obtained compound (3) and the compound ( It is preferable that the process (2) which obtains a compound (1) by making 4) react is included.
Step (1): A step of halogenating a compound represented by the following formula (2) to obtain a compound represented by the following formula (3).
R ^1- (A ¹ ) _a -Z ^1- (A ² ) _b -Z ^2- (A ³ ) _c -Z ³ -A ⁴ -CH ₂ CF = CF ₂ (2)
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH 2 CFX 1 CF 2 X 2 (3)
Step (2): A step of obtaining a liquid crystal compound represented by the formula (1) by reacting a compound represented by the following formula (4) with the compound represented by the formula (3).
Y ¹ O—A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e —R ² (4)
R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , Z ¹ , Z ² , Z in Formula (2), Formula (3) and Formula (4) ³ , Z ⁴ , Z ⁵ , a, b, c, d and e are the same as those in the above-mentioned compound (1) in the previous definition and preferred embodiments. X ¹ and X ² are halogen atoms, and Y ¹ is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.
X ¹ and X ² are preferably a bromine atom or an iodine atom from the viewpoint of reactivity.

  The compound (2) which is the starting material of the present invention can be obtained, for example, by the method described in JP-A-2008-19225.

  The reagent for halogenating compound (2) is not limited, but chlorine, bromine, iodine, N-bromosuccinimide, N, N'-dibromo-5,5-dimethylhydantoin, and N-iodosuccinimide are preferable.

  The amount of the halogenating reagent to be used is preferably 0.9 to 5.0 mol, more preferably 1 to 2 mol, per 1 mol of compound (2).

  The production process (1) of the present invention is preferably carried out in a solvent. Solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether, and t-butylmethyl. Ether solvents such as ether and dimethoxyethane; halogen solvents such as methylene chloride, 1,2-dichloromethane and chloroform; petroleum ethers or a suitable mixed solvent of the above solvents can be used. Among these, ether solvents such as diethyl ether and t-butyl methyl ether, halogen solvents, ether solvents and aliphatic hydrocarbon solvents are preferable.

  The amount of the solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate.

  The reaction temperature is preferably -70 to 50 ° C, more preferably -10 to 30 ° C.

  The reaction time is preferably 0.1 to 24 hours, more preferably 0.1 to 3 hours.

In this production method, the compound (2) is preferably the following compound (2-1), and the compound (3) is preferably the following compound (3-1).
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH 2 CF = CF 2 (2-1)
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH 2 CFX 11 CF 2 X 21 (3-1)
X ¹¹ and X ²¹ in the formula are a bromine atom or an iodine atom, and the symbols in each formula have the same meaning as described above.

In the production method of the present invention, it is particularly preferable that the compound (2) is the following compound (2-2) and the compound (3) is the following compound (3-2).
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH 2 CF = CF 2 (2-2)
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH 2 CFX 11 CF 2 X 21 (3-2)
The symbols in each formula have the same meaning as described above.

  The compound (4) can be easily obtained by a method described in an organic synthesis book such as a commercially available product or a new experimental chemical course (published by Maruzen Co., Ltd.).

  0.9-5.0 mol is preferable with respect to 1 mol of compound (3), and, as for the usage-amount of a compound (4), 1-2 mol is more preferable.

  Step (2) of the present invention is preferably carried out using a base. Bases include alkali metal hydroxides, hydrides, alkylates, alkoxides, amides or carbonates. In addition, an amine can be used.

  The step (2) of the present invention is preferably carried out in a solvent. Solvents include water, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether, t -Ether solvents such as butyl methyl ether and dimethoxyethane; aprotic polar solvents such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO); petroleum ethers or a suitable mixed solvent of the above solvents be able to. Among these, ether solvents such as diethyl ether and t-butyl methyl ether, aprotic polar solvents such as DMF and DMSO, mixed solvents of ether solvents and aliphatic hydrocarbon solvents, water and aliphatic hydrocarbon systems A mixed solvent of solvents is preferred.

  The amount of the solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate.

  The reaction temperature is preferably -70 to 200 ° C, more preferably -10 to 130 ° C.

  The reaction time is preferably 0.1 to 24 hours, more preferably 1 to 3 hours.

In the manufacturing method of this invention, the case where a compound (3) is the following compound (3-1) and a compound (4) is the following compound (4-1) is preferable.
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH 2 CFX 1 CF 2 X 2 (3-1)
^{Y 1 O-A 51 -Z 41} - (A 61) d -Z 51 - (A 71) e -R 21 (4-1)
The symbols in each formula have the same meaning as described above.

Moreover, in the manufacturing method of this invention, the case where a compound (3) is the following compound (3-2) and a compound (4) is the following compound (4-2) is especially preferable.
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH 2 CFX 1 CF 2 X 2 (3-2)
Y ¹ O—A ⁵² —Z ⁴² — (A ⁶² ) _d —Z ⁵² — (A ⁷² ) _e —R ²² (4-2)
The symbols in each formula have the same meaning as described above.

  The present invention also provides a liquid crystal composition comprising the compound (1). This liquid crystal composition is constituted by mixing the compound (1) of the present invention with other liquid crystal compounds or non-liquid crystal compounds (collectively referred to as “other compounds”).

  The content of the compound (1) in the liquid crystal composition of the present invention can be appropriately changed depending on the purpose of use, the purpose of use, the type of other compounds, and the like. 5-50 mass% is preferable, and 2-20 mass% is especially preferable. Moreover, you may contain 2 or more types of compounds (1) in a liquid-crystal composition by a use, a use purpose, etc. In that case, 0.5-80 mass% is preferable with the total amount of a compound (1) with respect to the whole quantity of a liquid-crystal composition, and 2-50 mass% is especially preferable.

  Other compounds used in combination with the compound (1) include components for adjusting the refractive index anisotropy value, components for reducing the viscosity, components exhibiting liquid crystallinity at low temperatures, components for improving the dielectric anisotropy, and cholesteric A component for imparting properties, a component exhibiting dichroism, a component for imparting conductivity, and various other additives. These are appropriately selected depending on the application, required performance and the like, but usually those composed of a liquid crystal compound, a main component having a similar structure to the liquid crystal compound, and an additive component added if necessary.

In the liquid crystal composition of the present invention, examples of the other compound include those represented by the following formulae. In the following formulae, R ³ and R ⁴ represent a group such as an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a halogen atom or a cyano group. R ³ and R ⁴ may be the same or different from each other.
In the following formulas, -Cy- represents a trans-1,4-cyclohexylene group, -Ph- represents a 1,4-phenylene group, and -PhFF- represents a difluorophenylene group.

R ³ -Cy-Cy-R ⁴
R ³ -Cy-Ph-R ⁴
R ³ -Cy-PhFF-CN
R ³ -Ph-Ph-R ⁴
R ³ —Ph—C≡C—Ph—R ⁴
R ³ -Cy-COO-Ph-R ^{4
R 3 -Cy-COO-PhFF-} CN
R ³ —Ph—COO—Ph—R ⁴
R ³ -Ph-COO-PhFF-CN
R ³ —Cy—CH═CH—Ph—R ⁴
R ³ —Ph—CH═CH—Ph—R ⁴
R ³ —Ph—CF═CF—Ph—R ⁴
R ³ —Cy—CF═CF—Ph—R ⁴
R ³ —Cy—CF═CF—Cy—R ⁴
R ³ —Cy—Ph—CF═CF—Ph—R ⁴
R ³ —Cy—Ph—CF═CF—Cy—R ⁴

R ³ —Ph—Cy—CF═CF—Cy—R ⁴
R ³ —Cy—Cy—CF═CF—Ph—R ⁴
R ³ —Ph—Ph—CF═CF—Ph—R ^{4
_{R 3 -Cy-CH 2 CH 2}} -Ph-R 4
_{^{R 3 -Cy-Ph-CH 2}} CH 2 -Ph-R 4
_{^{R 3 -Cy-Ph-CH 2}} CH 2 -Cy-R 4
_{^{R 3 -Cy-Cy-CH 2}} CH 2 -Ph-R 4
_{^{R 3 -Ph-CH 2 CH 2}} -Ph-R 4
_{^{R 3 -Ph-Ph-CH 2}} CH 2 -Ph-R 4
_{^{R 3 -Ph-Ph-CH 2}} CH 2 -Cy-R 4
R ³ -Cy-Ph-Ph-R ⁴
R ³ -Cy-Ph-PhFF-CN
R ³ -Cy-Ph-C≡C-Ph-R ⁴
R ³ -Cy-Ph-C≡C-PhFF-CN
R ³ -Cy-Ph-C≡C-Ph-Cy-R ⁴
R ³ —Cy—CH ₂ CH ₂ —Ph—C≡C—Ph—R ⁴

R ³ —Cy—CH ₂ CH ₂ —Ph—C≡C—Ph—Cy—R ⁴
R ³ -Cy-Ph-Ph-Cy-R ⁴
R ³ -Ph-Ph-Ph-R ⁴
R ³ —Ph—Ph—C≡C—Ph—R ⁴
R ³ —Ph—CH ₂ CH ₂ —Ph—C≡C—Ph—R ⁴
R ³ —Ph—CH ₂ CH ₂ —Ph—C≡C—Ph—Cy—R ^{4
R 3 -Cy-COO-Ph-} Ph-R 4
^{R 3 -Cy-COO-Ph-} PhFF-CN
^{R 3 -Cy-Ph-COO-} Ph-R 4
^{R 3 -Cy-Ph-COO-} PhFF-CN
^{R 3 -Cy-COO-Ph-} COO-Ph-R
^{R 3 -Cy-COO-Ph-} COO-PhFF-CN
^{R 3 -Ph-COO-Ph-} COO-Ph-R 4
^{R 3 -Ph-COO-Ph-} OCO-Ph-R 4
R ³ —Ph—CF ₂ O—Ph—R ⁴

R ³ —Cy—CF ₂ O—Ph—R ⁴
R ³ —Ph—CF ₂ O—Cy—R ^{4
_{R 3 -Cy-Ph-CF 2}} O-Ph-R 4
_{^{R 3 -Cy-Ph-CF 2}} O-Cy-R 4
_{^{R 3 -Cy-Cy-CF 2}} O-Ph-R 4
_{^{R 3 -Ph-Ph-CF 2}} O-Ph-R 4
_{^{R 3 -Ph-Ph-CF 2}} O-Cy-R 4
_{^{R 3 -Cy-Ph-CF 2}} O-PhFF-R 4
R ³ -Cy-PhFF-CF ₂ O-PhFF-R ^{4
_{R 3 -Ph-Ph-CF 2}} O-PhFF-R 4
R ³ -Ph-PhFF-CF ₂ O-PhFF-R ^{4
_{R 3 -Ph-CF 2 CF 2}} -Ph-R 4

^{_{R 3 -Cy-CF 2 CF 2}} -Ph-R 4
R ³ —Cy—CF ₂ CF ₂ —Cy—R ^{4
_{R 3 -Cy-Ph-CF 2}} CF 2 -Ph-R 4
_{^{R 3 -Cy-Ph-CF 2}} CF 2 -Cy-R 4
_{^{R 3 -Cy-Cy-CF 2}} CF 2 -Ph-R 4
_{^{R 3 -Ph-Ph-CF 2}} CF 2 -Ph-R 4
_{^{R 3 -Ph-Ph-CF 2}} CF 2 -Cy-R 4

These compounds are merely representative examples, and a hydrogen atom present in a ring structure or a terminal group in the compound may be substituted with a halogen atom, a cyano group, a methyl group, or the like. In addition, the cyclohexane ring or the benzene ring may be substituted with another 6-membered ring or 5-membered ring, for example, a pyrimidine ring or a dioxane ring. Changed to a divalent linking group such as —CH ₂ O—, —CH═CH—, —N═N—, —CH═N—, —COOCH ₂ —, —OCOCH ₂ — or —COCH ₂ —, etc. It can be selected according to the desired performance.

  Furthermore, the present invention provides a liquid crystal electro-optical element that uses the liquid crystal composition as a constituent material of a liquid crystal layer. In this specification, the liquid crystal electro-optical element is not limited to a display element, but various functional elements that use the electrical or optical characteristics of liquid crystal, for example, a liquid crystal display element, a light control window, an optical shutter, and a polarization It includes elements used for applications such as conversion elements and variable focus lenses. For example, a liquid crystal electro-optical element having an electro-optical element portion formed by sandwiching a liquid crystal layer formed by, for example, injecting the liquid crystal composition of the present invention into a liquid crystal cell between two substrates having electrodes. I will provide a. This liquid crystal electro-optic element is a twisted nematic (TN) method, a super twisted nematic (STN) method, an ECB mode, a VA mode, a guest host method, a dynamic scattering method, a phase change method, a DAP method, a dual frequency drive method, a strong Examples include those driven in various modes such as a dielectric liquid crystal display system.

A typical liquid crystal electro-optic element includes a twisted nematic (TN) type liquid crystal display element. The twisted nematic (TN) type liquid crystal display device, first, plastics, onto a substrate such as glass, of SiO _2, Al ₂ O undercoat layer or a color filter layer, such as ₃ to form optionally, an In ₂ O _A film made of _3- SnO ₂ (ITO), SnO ₂ or the like is formed, and an electrode having a required pattern is formed by photolithography or the like. Next, if necessary, an overcoat layer of polyimide, polyamide, SiO ₂ , Al ₂ O ₃ or the like is formed and oriented. A sealing material is printed on this, it arrange | positions so that an electrode surface may mutually oppose, a periphery is sealed, a sealing material is hardened, and an empty cell is formed.

  Furthermore, the composition of the present invention is injected into an empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, this liquid crystal cell is laminated with a polarizing plate, a color polarizing plate, a light source, a color filter, a transflective plate, a reflecting plate, a light guide plate, an ultraviolet cut filter, etc., printing characters, figures, etc., non-glare processing, etc. Thus, a liquid crystal electro-optical element can be obtained.

  Note that the above description describes the basic configuration and manufacturing method of the liquid crystal electro-optical element, and other configurations can be employed. For example, a substrate using a two-layer electrode, a two-layer liquid crystal cell having a two-layer liquid crystal layer, a substrate using a reflective electrode, an active matrix device using an active matrix substrate having an active element such as a TFT or MIM, etc. Various configurations can be employed.

  Furthermore, the composition of the present invention is a mode other than the TN type, that is, a high twist angle STN type liquid crystal electro-optical element, a guest-host (GH) type liquid crystal electro-optical element using a pleochroic dye, In-plane switching (IPS) type liquid crystal electro-optical element that drives liquid crystal molecules parallel to the substrate by a direction electric field, VA type liquid crystal electro-optical element that aligns liquid crystal molecules vertically with respect to the substrate, ferroelectric liquid crystal electro-optics It can be used in various ways such as an element. Further, it can be used not only in a method of electrically writing but also in a method of writing by heat.

Hereinafter, the present invention will be described more specifically with reference to examples. The following examples are intended to illustrate the present invention without limiting the present invention.

(Example 1)
Step (1): Synthesis of Compound (3A)

A mixture of 8.67 g of N-bromosuccinimide (NBS), 10.11 g of bromine and 100 mL of methylene chloride was cooled in an ice bath, and then a mixture of 25.09 g of compound (2A) and 50 mL of methylene chloride was added over about 30 minutes. And dripped. Thereafter, the mixture was warmed to room temperature, stirred for 2 hours, 100 mL of water was added dropwise, the reaction crude oil was washed with 5% aqueous sodium thiosulfate solution and water, and then concentrated to obtain 26.89 g of Compound (3A). .

Step (2): Synthesis of Compound (1A)

A mixture of 16.69 g of compound (3A), 3.89 g of compound (4A), 10.59 g of potassium carbonate, and 110 mL of DMF was heated to 110 ° C. and stirred for 3 hours. Then, it stirred at 80 degreeC overnight, 1.89 g of compounds (4A) and 1.57 g of potassium carbonate were added, and it stirred at 120 degreeC for 8 hours. After cooling to room temperature, it was quenched with water, the organic layer was extracted with hexane, treated with 5% aqueous sodium hydrogen carbonate solution and water, and then concentrated. The resulting crude product was purified by silica chromatography and recrystallization to obtain 2.95 g of compound (1A).

The NMR and phase series of the obtained compound (1A) are shown below.
<NMR>
¹⁹ F-NMR (282.6 MHz, heavy solvent CDCl ₃ , reference CFCl ₃ ) δ (ppm): −76.03 (d, 2F), −132.80 (m, 2F), −135.56 (m, 1F), -163.44 (m, 1F).
¹ H NMR (282.6 MHz, deuterated solvent CDCl ₃ , reference SiMe ₄ ) δ (ppm): 6.84 (m, 2H), 5.29 (dd, 1H), 2.8-0.7 (m, br).
<Phase series>
C 33.0 N 47.7 I (C: crystal, N: nematic phase, I: isotropic phase)

  Moreover, the following physical property was measured about the compound (1A) using liquid crystal composition ZLI-1565 by Merck as a mother liquid crystal. The results are shown in Table 1.

[Clear point]
Place the sample (mixture of the target compound and mother liquid crystal) on the hot plate (Mettler FP-82HT type hot stage) of the melting point measuring apparatus equipped with a polarizing microscope and heat the polarizing microscope while heating at a rate of 1 ° C / min. Observed. The temperature when a part of the sample was changed from a liquid crystal phase to an isotropic liquid was determined by extrapolation as a clearing point (Tc).
[Measurement of refractive index anisotropy (Δn)]
The refractive index anisotropy (Δn) at 25 ° C. was determined by extrapolation using a mixture of 20% by mass of the compound (1A) and 80% by mass of the mother liquid crystals.

[Measurement of dielectric anisotropy (Δε)]
A mixture of 10 mol% of the compound (1A) and 90 mol% of the mother liquid crystals was sealed between two glass cells (interval of 8 μm). A voltage of 100 mV was applied to the cell, and the dielectric constant (ε _⊥ ) in the minor axis direction of the liquid crystal molecules was measured. A voltage of 88 V was applied to measure the dielectric constant (ε _‖ ) in the major axis direction of the liquid crystal molecules.
Dielectric anisotropy of the compound ([Delta] [epsilon]) is seeking [Delta] [epsilon] of the composition from the equation [Delta] [epsilon] = epsilon _{‖-epsilon ⊥,} was determined by extrapolation.
When Δε at 0.85 Tc was determined, it was 7.43. Here, 0.85 Tc is a temperature (K) obtained by multiplying Tc (converted to absolute temperature (K)) of the liquid crystal composition by 0.85.

[Measurement of bulk viscosity]
A liquid crystal composition comprising 80% by mass of the mother liquid crystal and 20% by mass of the compound (1A) was prepared, measured at 25 ° C. and 0 ° C. using an E-type viscometer, and calculated by extrapolation. However, it was 54.0 mPa · s at 25 ° C. and 109.5 mPa · s at 0 ° C.

As described above, it has been found that the fluorine-containing liquid crystal compound of the present invention has sufficient values for the viscosity, Δε, Tc, and Δn to be used as components of the liquid crystal composition.
It has been clarified that by using such a compound of the present invention for a liquid crystal composition, a composition having various performances required for a liquid crystal element can be prepared.

(Example 2)
Based on Example 1 and the scheme described above, the following compounds can be prepared. In the following formulae, -Cy- and -Ph- are the same as described above, and other symbols have the following meanings.
-Ph (2F)-: 2-fluoro-1,4-phenylene group-Ph (2F, 6F)-: 2,6-difluoro-1,4-phenylene group-Ph (2F, 3F)-: 2,3 -Difluoro-1,4-phenylene group Moreover, the substitution position of the substituted ring group corresponding to A ^{1 to} A ⁷ in the formula (1) is always the 4-position when the ring member carbon is closer to R ¹ , R ² This is equivalent to the case where the one near is always the first place.

  Examples of the bicyclic compound (where all of a to e are 0) include the following.

C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-C ₂ H ₅
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -NCS
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -SF ₅
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ O-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₂ H ₅ -Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OCH ₃
C ₅ H ₁₁ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₂ H
CH ₃ CH = CH-C ₂ H ₄ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
CH ₃ OCH ₂ -Ph-CH = CFCF ₂ O-Ph (2F, 3F) -F
C ₃ H ₇ O-Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -F

C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph-C ₂ H ₅
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₃ H ₇ O-Cy-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₂ H ₅ -Cy-CH = CFCF ₂ O-Ph (2F, 3F) -OCH ₃
CH ₃ CH = CH-C ₂ H ₄ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -F
CH ₂ = CH-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₅ H ₁₁ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₂ H

  Examples of the tricyclic compound (one in which any one of a to e is 1 and the other 3 are 0) include the following.

C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-C ₂ H ₅
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-F
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₂ H ₅ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -NCS
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -SF ₅
C ₅ H ₁₁ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₃
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₂ H ₅ -Cy-Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Cy-Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₃
C ₃ H ₇ -Cy-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN

C ₂ H ₅ -Ph-Ph-CH = CFCF ₂ O-Ph-F
C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₅ H ₁₁ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -NCS
C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -SF ₅
C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₃
C ₂ H ₅ -Ph-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Ph-Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Ph-Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₅ H ₁₁ -Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F

C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-F
CH ₂ = CH-Cy-Cy-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₅ H ₁₁ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₂ H

C ₂ H ₅ -Ph-CH = CFCF ₂ O-Ph-Ph (2F) -F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -F
C ₅ H ₁₁ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -CN
CH ₃ CH = CHC ₂ H ₄ -Ph-CH = CFCF ₂ O-Ph-Ph (2F) -F
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-Ph (2F, 3F) -OCH ₃
C ₃ H ₇ -Ph (2F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₂ H ₅ -Ph-CH = CFCF ₂ O-Ph-Cy-C ₅ H ₁₁
C ₂ H ₅ -Ph-CH = CFCF ₂ O-Ph (2F) -Cy-C ₅ H ₁₁
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Cy-C ₅ H ₁₁
C ₃ H ₇ -Ph (2F, 3F) -CH = CFCF ₂ O-Ph-Cy-OC ₂ H ₅
C ₂ H ₅ -Cy-CH = CFCF ₂ O-Ph-Ph (2F) -F
C ₅ H ₁₁ -Cy-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -F
C ₅ H ₁₁ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -CN
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph-Ph (2F, 3F) -OC ₂ H ₅

C ₃ H ₇ -Cy-C ₂ H ₄ -Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Cy-C ₂ H ₄ -Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-C ₂ H ₄ -Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -OCF ₃
CH ₃ CH = CHC ₂ H ₄ -Cy-C ₂ H ₄ -Ph-CH = CFCF ₂ O-Ph (2F) -C ₃ H ₇
CH ₂ = CH-Cy-CH ₂ O-Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Cy-CH ₂ O-Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅

  Examples of the tetracyclic compound (one in which any two of a to e are 1 and the other two are 0) include the following.

C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-Ph-Ph-C ₂ H ₅
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
C ₂ H ₅ -Ph-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -Ph (2F) -F
C ₅ H ₁₁ -Ph-CH = CFCF ₂ O-Ph (2F) -Ph (2F) -Ph (2F) -CN
C ₅ H ₁₁ -Ph-CH = CFCF ₂ O-Ph (2F) -Ph (2F, 6F) -Ph (2F) -OCF ₃
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -Ph (2F, 6F) -F
C ₂ H ₅ -Ph (2F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -Ph (2F) -CN
C ₂ H ₅ -Ph (2F, 3F) -CH = CFCF ₂ O-Ph-Ph-Ph (2F) -F

C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph-Ph-Ph-C ₂ H ₅
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
C ₂ H ₅ -Cy-CH = CFCF ₂ O-Ph-Ph (2F, 3F) -Ph (2F, 3F) -OC ₂ H ₅
C ₅ H ₁₁ -Cy-CH = CFCF ₂ O-Ph (2F) -Ph (2F) -Ph (2F) -CN
C ₅ H ₁₁ -Cy-CH = CFCF ₂ O-Ph (2F) -Ph (2F, 6F) -Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -Ph (2F, 6F) -F
C ₂ H ₅ -Cy-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -Ph (2F) -CN

C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 3F) -Ph (2F, 3F) -Cy-C ₂ H ₅
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -Cy-CH = CH ₂
C ₃ H ₇ -Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -Ph (2F, 3F) -Cy-CH ₃
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 3F) -Cy-Cy-C ₂ H ₅
C ₃ H ₇ -Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Cy-Cy-OCH ₃

C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-Ph-C ₂ H ₅
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph (2F) -Ph (2F, 6F) -F
C ₅ H ₁₁ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -Ph (2F, 6F) -OCF ₃
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-Cy-CH = CH ₂
C ₅ H ₁₁ -Cy-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -Cy-C ₂ H ₅
C ₃ H ₇ -Cy-Ph (2F, 3F) -CH = CFCF ₂ O-Ph (2F, 3F) -Cy-C ₂ H ₅
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Ph (2F) -F
C ₅ H ₁₁ -Cy-Cy-CH = CFCF ₂ O-Ph (2F) -Ph (2F, 6F) -CN
C ₅ H ₁₁ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 3F) -Ph (2F, 3F) -OC ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-CH = CFCF ₂ O-Ph (2F) -Cy-C ₃ H ₇
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -Cy-OC ₂ H ₅
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph (2F, 3F) -Cy-OCH ₃

C ₃ H ₇ -Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Ph-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Ph-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₂ H ₅ -Ph-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph (2F) -CN
CH ₃ -CH = CH-C ₂ H ₄ -Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F
CH ₂ = CH-Cy-Cy-Cy-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Cy-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Cy-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₂ H ₅ O-Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₃ H ₇ -Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₂ H ₅ -Cy-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph (2F) -CN
CH ₂ = CH-Cy-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F

  Examples of the pentacyclic compound (one in which any three of a to e are 1 and the other two are 0) include the following.

C ₃ H ₇ -Ph-Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F
C ₃ H ₇ -Ph-Ph-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Ph-Ph-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₂ H ₅ -Ph-Ph-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph (2F) -CN
CH ₃ -CH = CH-C ₂ H ₄ -Ph-Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F
CH ₂ = CH-Cy-Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Cy-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₂ H ₅ O-Cy-Cy-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Ph-Ph (2F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₃ H ₇ -Cy-Cy-Ph-Ph-CH = CFCF ₂ O-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Ph-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph (2F, 6F) -CN
C ₂ H ₅ -Cy-Ph-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph (2F) -CN
C ₃ H ₇ -Cy-Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F, 6F) -F
CH ₂ = CH-Cy-Ph-Ph-Ph-CH = CFCF ₂ O-Ph (2F) -F

C ₃ H ₇ -Ph-Ph-Ph-CH = CFCF ₂ O-Ph-Ph (2F) -F
C ₃ H ₇ -Ph-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Ph-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -CN
C ₂ H ₅ -Ph-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph-Ph (2F) -CN
CH ₃ -CH = CH-C ₂ H ₄ -Ph-Ph-Ph-CH = CFCF ₂ O-Ph-Ph (2F) -F
CH ₂ = CH-Cy-Cy-Cy-CH = CFCF ₂ O-Ph-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Cy-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Cy-CH = CFCF ₂ O-Ph-Ph (2F, 3F) -OC ₂ H ₅
C ₂ H ₅ O-Cy-Cy-Ph-CH = CFCF ₂ O-Ph-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-Ph-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-Ph (2F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -CN
C ₃ H ₇ -Cy-Cy-Ph-CH = CFCF ₂ O-Ph-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Ph-CH = CFCF ₂ O-Ph-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -CN
C ₂ H ₅ -Cy-Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph-Ph (2F) -CN
C ₃ H ₇ -Cy-Ph-Ph-CH = CFCF ₂ O-Ph-Ph (2F, 6F) -F
CH ₂ = CH-Cy-Ph-Ph-CH = CFCF ₂ O-Ph-Ph (2F) -F

C ₃ H ₇ -Ph-Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -F
C ₃ H ₇ -Ph-Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Ph (2F) -Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -CN
C ₂ H ₅ -Ph (2F, 6F) -Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -CN
CH ₃ -CH = CH-C ₂ H ₄ -Ph-Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -F
CH ₂ = CH-Cy-Cy-CH = CFCF ₂ O-Ph-Cy-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Cy-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Cy-Ph (2F, 3F) -OC ₂ H ₅
C ₂ H ₅ O-Cy-Cy-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Ph (2F) -Ph (2F, 6F) -CN
C ₃ H ₇ -Cy-Cy-CH = CFCF ₂ O-Ph-Ph-Ph (2F, 3F) -OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -OCF ₃
C ₃ H ₇ -Cy-Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
C ₃ H ₇ -Cy-Ph (2F) -CH = CFCF ₂ O-Ph-Ph (2F, 6F) -Ph (2F, 6F) -CN
C ₂ H ₅ -Cy-Ph (2F, 6F) -CH = CFCF ₂ O-Ph-Ph-Ph (2F) -CN
C ₃ H ₇ -Cy-Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F, 6F) -F
CH ₂ = CH-Cy-Ph-CH = CFCF ₂ O-Ph-Ph-Ph (2F) -F

Claims (7)

A liquid crystal compound represented by the following formula (1).
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH = CFCF 2 O-A 5 -Z 4 - (A 6) d _{^{-Z 5 - (A 7) e}} -R 2 (1)
The symbol in Formula (1) shows the following meanings.
R ¹ and R ^{2 are} each independently a hydrogen atom, a halogen atom, —CN, —NCS, —SF ₅ or a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and one of the groups more -CH ₂ - may etheric oxygen atom may be substituted by thioether sulfur atoms, any hydrogen atom in the group may be substituted with a fluorine atom.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ : independently of each other, trans-1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1, 3 -Cyclobutylene group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group Or 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. Two —CH ₂ — groups may be substituted with an etheric oxygen atom or a thioetheric sulfur atom.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ : each independently a single bond, a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and one or more —CH in the group ₂ - is an etheric oxygen atom may be substituted by thioether sulfur atoms, any hydrogen atom in the group may be substituted with a fluorine atom.
a, b, c, d, e: 0 or 1 independently of each other. However, 0 ≦ a + b + c + d + e ≦ 3. The liquid crystal compound according to claim 1 represented by the following formula (1-1).
_{^{R 11 - (A 11) a}} -Z 11 - (A 21) b -Z 21 - (A 31) c -Z 31 -A 41 -CH = CFCF 2 O-A 51 -Z 41 - (A 61) d _{^{-Z 51 - (A 71) e}} -R 21 (1-1)
The symbols in the formula have the following meanings.
R ¹¹ and R ^{21 are} each independently a hydrogen atom, a fluorine atom, —SF ₅ , an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. One or more —CH ₂ — in the group may be substituted with an etheric oxygen atom or a thioetheric sulfur atom, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ : Independently of each other, a trans-1,4-cyclohexylene group or a 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. One —CH ₂ — group may be substituted with an etheric oxygen atom or an etheric sulfur atom.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ^{51 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and one or more —CH ₂ — in the group is an etheric oxygen An atom may be substituted, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
a, b, c, d and e have the same meaning as in formula (1). The liquid crystal compound according to claim 1 represented by the following formula (1-2).
_{^{R 12 - (A 12) a}} -Z 12 - (A 22) b -Z 22 - (A 32) c -Z 32 -A 42 -CH = CFCF 2 O-A 52 -Z 42 - (A 62) d _{^{-Z 52 - (A 72) e}} -R 22 (1-2)
The symbols in the formula have the following meanings.
R ¹² : a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. One or more —CH ₂ — in the group may be substituted with an etheric oxygen atom, and one or more hydrogen atoms in the group may be substituted with fluorine.
R ²² : a hydrogen atom, a fluorine atom, —SF ₅ , or an alkyl group having 1 to 18 carbon atoms. One or more —CH ₂ — in the group may be substituted with an etheric oxygen atom, and one or more hydrogen atoms in the group may be substituted with a fluorine atom.
A ¹² , A ²² , A ³² , A ⁴² , A ⁵² , A ⁶² , A ⁷² : independently of each other, trans-1,4-cyclohexylene group, 1,4-phenylene group, or one or two of them 1,4-phenylene group substituted by a fluorine atom.
Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² : each independently a single bond, an alkylene group having 1 to 4 carbon atoms.
a, b, c, d and e have the same meaning as in formula (1). The manufacturing method of the liquid-crystal compound of Claim 1 including the following process (1) and process (2).
Step (1): A step of halogenating a compound represented by the following formula (2) to obtain a compound represented by the following formula (3).
R ^1- (A ¹ ) _a -Z ^1- (A ² ) _b -Z ^2- (A ³ ) _c -Z ³ -A ⁴ -CH ₂ CF = CF ₂ (2)
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH 2 CFX 1 CF 2 X 2 (3)
Step (2): A step of obtaining a liquid crystal compound represented by the formula (1) by reacting a compound represented by the following formula (4) with the compound represented by the formula (3).
Y ¹ O—A ⁵ —Z ⁴ — (A ⁶ ) _d —Z ⁵ — (A ⁷ ) _e —R ² (4)
In each formula,
R ¹ , R ² , A ^{1 to} A ⁷ , Z ^{1 to} Z ^5, and a to e are the same as defined in the formula (1) in claim 1.
X ¹ and X ² : a halogen atom.
Y ¹ : a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. A compound represented by the following formula (3).
_{^{R 1 - (A 1) a}} -Z 1 - (A 2) b -Z 2 - (A 3) c -Z 3 -A 4 -CH 2 CFX 1 CF 2 X 2 (3)
Where
R ^{1 is a} hydrogen atom, a halogen atom, —CN, —NCS, —SF ₅ or a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and one or more —CH ₂ — in the group is an ether An oxygen atom or a thioetheric sulfur atom, and any hydrogen atom in the group may be substituted with a fluorine atom.
A ^{1 to} A ⁴ : independently of each other, trans-1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclobutylene group, 1,2-cyclopropylene group, naphthalene- 2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,4-phenylene group. One or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two ═CH— groups present in the group may be substituted with a nitrogen atom. Two —CH ₂ — groups may be substituted with an etheric oxygen atom or a thioetheric sulfur atom.
Z ^{1 to} Z ^{3 are} each independently a single bond, a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and one or more —CH ₂ — in the group is an etheric oxygen atom, It may be substituted with a thioetheric sulfur atom, and any hydrogen atom in the group may be substituted with a fluorine atom.
a, b, c, d, e: 0 or 1 independently of each other. However, 0 ≦ a + b + c + d + e ≦ 3.
X ¹ and X ² : a halogen atom.   A liquid crystal composition comprising the liquid crystal compound according to claim 1.   A liquid crystal electro-optical element formed by sealing the liquid crystal composition according to claim 6 between two substrates provided with electrodes.