JP2012106969A - Liquid crystal compound, method for producing the same, liquid crystal composition and liquid crystal electrooptical element - Google Patents

Abstract

A novel liquid crystal compound having a low viscosity, a high clearing point, and a chemically stable liquid crystal composition, a liquid crystal composition satisfying conditions such as a manufacturing method, high-speed response, and a wide operating temperature range, and a high-speed response in a wide temperature range Providing liquid crystal electro-optic elements with excellent properties.
SOLUTION: Formula (1) R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH = CH-A A liquid crystal compound represented by ^5- (Z ⁴ -A ⁶ ) _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² . R ¹ , R ² : a hydrogen atom, a halogen atom, or a monovalent acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms. A ^{1 to} A ⁸ : cyclic groups such as trans-1,4-cyclohexylene group and 1,4-phenylene group. Z ^{1 to} Z ⁶ : a single bond, —O—, —S—, —COO— or a divalent acyclic aliphatic hydrocarbon group having 1 to 4 carbon atoms. m, n, o, p, q, r: 0 or 1 independently of each other (provided that m + n + o + p + q + r ≦ 3). The hydrogen atom in each of the above groups may be substituted with a halogen atom. -O- or -S- may be inserted between carbon-carbon atoms in the mono- or divalent acyclic aliphatic hydrocarbon group or at the bond terminal of the group. The ═CH— group in the ring group may be a nitrogen atom, and the —CH ₂ — group may be substituted with —O— or —S—.
[Selection figure] None

Description

  The present invention relates to a novel fluorine-containing liquid crystal compound, a liquid crystal composition containing the compound, a liquid crystal electro-optical element containing the liquid crystal composition, and a method for producing the compound.

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 having a property of being excellent in high-speed response and being driven at a low voltage in a wide temperature range when used in the above.

As a solution to such a problem, for example, a stilbene compound having a —CF═CF— linking group has been reported (Patent Document 1). This compound has a feature that the viscosity is low and the response speed is high when used in a liquid crystal display device, but there is a problem that it is unstable with respect to light and an ultraviolet cut filter or the like must be used in combination.
In addition, compounds having a —CH═CHCH ₂ CH ₂ — linking group have been reported (Patent Documents 2 and 3). This compound is also said to have a feature such as low viscosity, but since it has a —CH═CH— moiety, it is considered that cis-trans isomerization is likely to occur.

  As described above, a compound used for a liquid crystal composition or the like often has a sacrifice of other performance when the specific performance is improved. Development is desired.

Japanese Patent Laid-Open No. 03-294386 JP-A-4-330019 Japanese Patent Laid-Open No. 10-7598

  An object of the present invention is to provide a novel fluorine-containing liquid crystal compound useful as a liquid crystal material. Another object of the present invention is to provide a liquid crystal composition containing the compound and a liquid crystal electro-optical element containing the liquid crystal composition. Furthermore, it aims at providing the manufacturing method which can utilize this compound industrially.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1), and compounds represented by other formulas are also described in the same manner. In the present specification, unless otherwise noted, the ^one closer to R ¹ in the formula (1) is always the first place.

In order to achieve the above object, the present invention provides compound (1).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH = CH-A ^5- (Z ⁴ -A ⁶ _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (1)
The symbols in the above formula have the following meanings.
R ¹ and R ² : independently of each other, a hydrogen atom, a halogen atom, or a monovalent acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms. However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and between the carbon-carbon atoms in the aliphatic hydrocarbon group or at the bond terminal of the aliphatic hydrocarbon group. , -O- or -S- may be inserted.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ : independently of each other, a trans-1,4-cyclohexylene group, a 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 -A diyl 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. Two —CH ₂ — groups may be substituted with —O— or —S—.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ : independently of each other, a single bond, —O—, —S—, —COO— or a divalent acyclic ring having 1 to 4 carbon atoms Formula aliphatic hydrocarbon group. However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and the bond terminal of the aliphatic hydrocarbon group or between carbon-carbon atoms in the aliphatic hydrocarbon group -O- or -S- may be inserted.
m, n, o, p, q, r: 0 or 1 independently of each other. However, m + n + o + p + q + r is 3 or less.
In addition, the above-mentioned -O- or -S- does not continue in the whole compound.

The compound (1) is preferably represented by the following formula (1-1).
^{R 11 - (A 11 -Z 11} ) m - (A 21 -Z 21) n - (A 31 -Z 31) o -A 41 -CF 2 CF 2 CH = CH-A 51 - (Z 41 -A 61 _p- (Z ⁵¹ -A ⁷¹ ) _q- (Z ⁶¹ -A ⁸¹ ) _r -R ²¹ (1-1)
The symbols in the above formula (1-1) have the following meanings.
R ¹¹ , R ²¹ : independently of each other, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with fluorine atoms, and —O— or —S— may be inserted between carbon-carbon atoms in the group or at the bond terminal of the group. .
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ , A ⁸¹ : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group. However, one or more hydrogen atoms present in the 1,4-phenylene group may be substituted with fluorine atoms.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁶¹ : independently of each other, a single bond, —O—, —S—, or an alkylene group having 1 to 4 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with a halogen atom, and —O— or —S— is inserted between carbon-carbon atoms in the group or at the bond terminal of the group. It may be.
m, n, o, p, q and r have the same meaning as described above.

Moreover, this invention provides the manufacturing method of the said compound (1) including the following process 1 and process 2.
Step 1: A step of producing the following compound (4) by an addition reaction between the following compound (2) and the following compound (3).
Step 2: A step of dehydrohalogenating the following compound (4) in the presence of a base to obtain the above compound (1).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
^{_{CH 2 = CH-A 5 -}} (Z 4 -A 6) p - (Z 5 -A 7) q - (Z 6 -A 8) r -R 2 (3)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH ₂ CHX ¹ -A ^5- (Z ⁴ -A ⁶ ) _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (4)
In the above formulas, X ¹ is a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , m, n, o, p, q, r have the same meaning as described above.

Moreover, this invention also provides the manufacturing method of a compound (1) by making a compound (2) and the following compound (5) react.
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
^{CHX 2 = CH-A 5 -} (Z 4 -A 6) p - (Z 5 -A 7) q - (Z 6 -A 8) r -R 2 (5)
In the above formulas, X ¹ and X ² are each independently a chlorine atom, bromine atom or iodine atom, and R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , m, n, o, p, q, r have the same meaning as described above.

  The present invention also provides a liquid crystal composition containing the compound (1).

  The present invention also provides a liquid crystal electro-optical element in which a liquid crystal composition containing the compound (1) is sandwiched between substrates with electrodes.

Since the compound (1) of the present invention has the characteristics of low viscosity, high clearing point, and chemical stability, a liquid crystal composition satisfying conditions such as high-speed response and a wide operating temperature range can be prepared. Also, when the liquid crystal composition is used in a liquid crystal electro-optical element, it has excellent high-speed response over a wide temperature range.
Furthermore, according to the production method of the present invention, the compound (1) of the present invention can be easily and easily synthesized industrially.

In the compound (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a monovalent acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms. However, in the aliphatic hydrocarbon group, one or more hydrogen atoms may be substituted with a halogen atom. Further, —O— or —S— may be inserted between carbon-carbon atoms in the aliphatic hydrocarbon group or at the bond terminal of the aliphatic hydrocarbon group. Note that the substitution with a halogen atom and the insertion of —O— or —S— may be simultaneously performed on the same aliphatic hydrocarbon group.

  Examples of the monovalent acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the group in which one or more hydrogen atoms in these groups are substituted with a halogen atom include a fluoroalkyl group and a chloroalkyl group. Furthermore, examples of the group in which —O— or —S— is inserted between carbon-carbon atoms in these groups include alkoxyalkyl groups and alkylthioalkyl groups. Moreover, an alkoxy group or an alkylthio group is mentioned as a group in which -O- or -S- is inserted at the bond terminal of the group. Further, examples of the group in which the substitution with a halogen atom and the insertion of —O— are performed on the same aliphatic hydrocarbon group include a fluoroalkoxy group. These groups may be either linear or branched, but are preferably linear.

Among the above, R ¹ and R ² are preferably a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. One or more hydrogen atoms in the alkyl group, alkenyl group or alkenyl group may be substituted with a fluorine atom, and —O— or —S— may be present between carbon-carbon atoms in the group or at the bond terminal of the group. It may be inserted.
As the halogen atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable.

Particularly preferred R ¹ and R ² are a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, an alkoxy group, a fluoroalkyl group, or a fluoroalkoxy group. Among these alkyl groups having 1 to 5 carbon atoms, an ethyl group, a propyl group, or a pentyl group is particularly preferable. Of the alkoxy groups having 1 to 5 carbon atoms, a methoxy group or an ethoxy group is particularly preferable. Of the fluoroalkyl groups having 1 to 5 carbon atoms, a trifluoromethyl group is particularly preferred. Of the fluoroalkoxy groups having 1 to 5 carbon atoms, a trifluoromethoxy group is particularly preferable.

In the formula (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are independently of each other a 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. However, one or more hydrogen atoms in the group may be substituted with a halogen atom, and one or two —CH═ present in the group may be substituted with a nitrogen atom. One or two —CH ₂ — present therein may be substituted with —O— or —S—. The halogen atom for the substitution is preferably a fluorine atom or a chlorine atom, particularly preferably a fluorine atom.

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are trans-1,4-cyclohexylene groups because the compounds have a linear structure and are easy to use for liquid crystals. 1,4-phenylene group is preferred. From the viewpoint of compatibility and dielectric anisotropy when used for liquid crystals, it is also preferred that at least one 1,4-phenylene group is substituted with one or more fluorine atoms. Examples of the 1,4-phenylene group substituted with one or more fluorine atoms include 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, and 2,3-difluoro-1 A 4-phenylene group is preferred.

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are each independently a single bond, —O—, —S—, —COO— or a divalent non-carbon group having 1 to 4 carbon atoms. A cycloaliphatic hydrocarbon group; However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and the bond terminal of the aliphatic hydrocarbon group or between carbon-carbon atoms in the aliphatic hydrocarbon group -O- or -S- may be inserted. Note that the substitution with a halogen atom and the insertion of —O— or —S— may be simultaneously performed on the same aliphatic hydrocarbon group.

When Z ¹ is a single bond, it means that the ring groups on both sides of Z ¹ are directly bonded. For example, when m and o are 1, Z ¹ is a single bond, and n is 0, A ¹ and A ³ are directly bonded. When m is 1, Z ¹ is a single bond and n is 1, A ¹ and A ² are directly bonded. The same applies to Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ .

  Examples of the divalent acyclic aliphatic hydrocarbon group having 1 to 4 carbon atoms include an alkylene group having 1 to 4 carbon atoms, an alkenylene group having 2 to 4 carbon atoms, and an alkynylene group having 2 to 4 carbon atoms. . Examples of the halogen atom include a fluorine atom or a chlorine atom. Examples of the group in which one or more hydrogen atoms in these groups are substituted with a halogen atom include a fluoroalkylene group, a chloroalkylene group, or a fluoroalkenylene group. Is mentioned. Further, groups in which —O— or —S— is inserted between carbon-carbon atoms in these groups or at the bond end of the group include oxyalkylene groups, alkyloxyalkylene groups, thioalkylene groups, oxyfluoroalkylenes. Group, or a thiofluoroalkylene group.

The alkylene group having 1 to 4 carbon _{atoms, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, and _{-CH 2 CH 2 CH 2 CH 2} - is like, especially - CH ₂ - or _-CH 2 CH ₂ - is preferred.

Examples of the alkenylene group having 2 to 4 carbon atoms include —CH═CH—, —CH═CH—CH ₂ —, —CH═CH—CH ₂ —CH ₂ —, —CH═CH—CH═CH—, and — CH ₂ —CH═CH—CH ₂ — and the like can be mentioned, and these groups may be reversed. -CH = CH- is particularly preferable.

Examples of the alkynylene group having 2 to 4 carbon atoms include —C≡C—, —C≡C—CH ₂ —, —C≡C—CH ₂ —CH ₂ —, —C≡C—C≡C—, and — CH ₂ —C≡C—CH ₂ — and the like, and further, a group in which a double bond and a triple bond are mixed, such as —CH═CH—C≡C—, is also included. These groups may be reversed. -C≡C- is particularly preferable.

The fluoroalkylene group, chloro alkylene groups and fluoro alkenylene group having 1 to 4 carbon _{atoms, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 CF 2 -, - CH 2 CF 2 -, —CF═CF—, —CCl ₂ CH ₂ —, —CF═CF—C≡C— and the like are mentioned, and —CF ₂ CF ₂ — or —CF═CF— is particularly preferable.

Examples of the oxyalkylene group having 1 to 4 carbon atoms, the thioalkylene group, the alkyloxyalkylene group, the oxyfluoroalkylene group, and the thiofluoroalkylene group include —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH _{2. S -, - CH 2 CH 2} OCH 2 -, - OCF 2 -, - SCF 2 -, - CF 2 O-, and _-CF 2 S- and the like, -OCF ₂ - or _-CF 2 O-is preferable.

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are each a single bond, —O—, —S—, or an alkylene group having 1 to 4 carbon atoms in view of stability of the compound and ease of synthesis. Is preferred. One or more hydrogen atoms in the alkylene group may be substituted with fluorine atoms, and -O- or -S- may be inserted between carbon-carbon atoms in the group or at the bond terminal of the group. Good. In particular, a single bond or an alkylene group having 1 to 4 carbon atoms is preferable, and a single bond is more preferable.

  In the compound (1), m, n, o, p, q and r are each independently 0 or 1. However, m + n + o + p + q + r is 3 or less. Since the viscosity is not so high, m + n + o + p + q + r is preferably 2 or less.

In general, in a compound having a linking group such as a group having a double bond such as —CH═CH— or —CF═CF—, when a phenyl group is bonded to the linking group, the compound is cis by ultraviolet light or visible light. -There is a problem that trans isomerization is likely to occur. A typical example is a compound having a stilbene structure. In contrast, the compound of the present invention having —CF ₂ CF ₂ CF═CF— as a linking group has a phenyl group at both ends of the double bond as in the case of a stilbene compound, even if a phenyl group is bonded to both ends of the linking group. Since the group is not present, the conjugated system is shortened and isomerization is unlikely to occur. Further, even when compared with the —CH═CHCH ₂ CH ₂ — linking group, it is considered that isomerization hardly occurs because the hydrogen atom of the —CH ₂ CH ₂ — moiety is substituted with a fluorine atom. From these facts, it is considered that the compound of the present invention is excellent in stability as compared with an existing compound having a group having a double bond as a linking group.

Among the compounds (1) of the present invention as described above, the following compound (1-1) is preferable.
^{R 11 - (A 11 -Z 11} ) m - (A 21 -Z 21) n - (A 31 -Z 31) o -A 41 -CF 2 CF 2 CH = CH-A 51 - (Z 41 -A 61 _p- (Z ⁵¹ -A ⁷¹ ) _q- (Z ⁶¹ -A ⁸¹ ) _r -R ²¹ (1-1)
The symbols in the above formula (1-1) have the following meanings.
R ¹¹ , R ²¹ : independently of each other, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with fluorine atoms, and —O— or —S— may be inserted between carbon-carbon atoms in the group or at the bond terminal of the group. .
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ , A ⁸¹ : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group. However, one or more hydrogen atoms present in the 1,4-phenylene group may be substituted with fluorine atoms.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁶¹ : independently of each other, a single bond, —O—, —S—, or an alkylene group having 1 to 4 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with a halogen atom, and —O— or —S— is inserted between carbon-carbon atoms in the group or at the bond terminal of the group. It may be.
m, n, o, p, q and r have the same meaning as described above, and the specific description of each group is as described above.

A more preferred compound (1) of the present invention is the following compound (1-2).
^{R 12 - (A 11 -Z 12} ) m - (A 21 -Z 22) n - (A 31 -Z 32) o -A 41 -CF 2 CF 2 CH = CH-A 51 - (Z 42 -A 61 _p- (Z ⁵² -A ⁷¹ ) _q- (Z ⁶² -A ⁸¹ ) _r -R ²² (1-2)
The symbols in the above formula (1-2) have the following meanings. R ¹² , R ²² : independently of each other, a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, an alkoxy group, a fluoroalkyl group, or a fluoroalkoxy group. Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² , Z ⁶² : each independently a single bond or an alkylene group having 1 to 4 carbon atoms. A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ , A ⁸¹ , m, n, o, p, q and r have the same meaning as described above, As described above.

Particularly preferred compound (1) of the present invention is the following compound (1-3).
_{^{R 13 - (A 11) m}} -A 41 -CF 2 CF 2 CH = CH-A 51 - (A 81) r -R 23 (1-3)
The symbols in the above formula (1-3) have the following meanings. R ¹³ and R ²³ : each independently a fluorine atom, a linear alkyl group having 1 to 5 carbon atoms, an alkoxy group, a fluoroalkyl group or a fluoroalkoxy group. A ¹¹ , A ⁴¹ , A ⁵¹ , A ⁸¹ , and m and r are independently 0 or 1, and the specific description of each group is also as described above.

The compound (1) of the present invention as described above can be produced, for example, by Production Method 1 or Production Method 2 shown below.
First, the manufacturing method 1 is demonstrated.
[Production Method 1] A production method of compound (1) comprising the following step 1 and step 2.
Step 1: A step of producing the following compound (4) by adding the compound (3) to the compound (2).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
^{_{CH 2 = CH-A 5 -}} (Z 4 -A 6) p - (Z 5 -A 7) q - (Z 6 -A 8) r -R 2 (3)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH ₂ CHX ¹ -A ^5- (Z ⁴ -A ⁶ ) _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (4)
Each symbol in the above formulas is the same as that in formula (1), and X ¹ is a chlorine atom, bromine atom or iodine atom.
Step 2: The above compound (4) is dehydrohalogenated in the presence of a base.

The compound (2) can be obtained based on a known method, and can be obtained, for example, according to the methods described in JP-A No. 2002-128776 and Journal of Fluorine Chemistry 2004, 125, 595-601.
For example, when the compound (2) is the following compound (2-1), it can be obtained by iodination of the carboxylic acid (6) by decarboxylation.
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n - (A 3 -Z 3) o -Cy-CF 2 CF 2 COOH (6)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n - (A 3 -Z 3) o -Cy-CF 2 CF 2 I (2-1)
When the compound (2) is the following compound (2-2), it can be obtained by fluorinating 2,2-difluoro-2-halo-acetaldehyde (7).
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n - (A 3 -Z 3) o -Ph-CO-CF 2 X (7)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n - (A 3 -Z 3) o -Ph-CF 2 CF 2 X (2-2)
In addition, -Cy- represents a trans-1,4-cyclohexylene group, -Ph- represents a 1,4-phenylene group, and X represents a halogen atom. Other symbols have the same meaning as described above.

  Compound (3) is also available as a commercial product. Also obtained based on methods described in documents of organic synthesis, such as documents such as Japanese Patent Application Laid-Open No. 08-170078 and Japanese Patent Application Laid-Open No. 10-114690, and a new experimental chemistry course (published by Maruzen Co., Ltd.). Can do.

  In step 1, compound (3) is usually used in an amount of 0.5 to 2 mol per 1 mol of compound (2).

In step 1, a radical addition reaction is usually performed.
Examples of the radical initiator that can be used in Step 1 include organic oxides such as di-tert-butyl peroxide, dibenzoyl peroxide, and diisopropyl peroxide, azobisisobutyronitrile, 1,1′-azobis ( Cyclohexane-1-carbonitrile), azo compounds such as 2,2-azobis (2-methylbutyronitrile), borane compounds such as triethylborane, copper salts, inorganic salts such as sodium hypothionite, [Pd (PPh ₃ ) ₄ ], metal complexes such as AlMe ₃ can be used. The same radical addition reaction can also be performed by light irradiation or heating.

  The amount of the radical initiator used is 0.00001 times to 1.0 times mol, preferably 0.001 times to 0.1 times mol, relative to compound (2).

Step 1 is performed without a solvent or in a solvent. Reaction 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, dibutyl ether, and t-butyl. Ether solvents such as methyl ether, amine solvents such as pyridine and triethylamine, nitrile solvents such as acetonitrile and benzonitrile, halogen solvents such as methylene chloride and 1,2-dichloroethane, N, N-dimethylformamide, dimethyl sulfoxide An aprotic polar solvent such as the above or a suitable mixed solvent of the above solvents can be used, but it is particularly preferable to carry out the reaction in the absence of a solvent or an aliphatic hydrocarbon solvent.
The amount of solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate.

  The temperature in step 1 is preferably from -100 ° C to 250 ° C, and particularly preferably from 50 ° C to 100 ° C.

  The reaction time of step 1 is preferably 0.5 to 48 hours, particularly preferably 0.5 to 8 hours.

Step 2 is a step of obtaining compound (1) by dehydrohalogenating compound (4) obtained in step 1 using a base.
Examples of the base include amines such as triethylamine and diazabicycloundecene, metal alkoxides such as potassium, tert-butoxide and sodium methoxide, alkali metal salts such as sodium hydroxide, sodium hydride, potassium hydroxide and potassium carbonate, Alkylated metals such as n-butyllithium and tert-butyllithium, and metal amides such as lithium hexamethyldisilazide and lithium diisopropylamide can be used. In particular, diazabicycloundecene and potassium hexamethyldisilazide are preferred.

  The base is usually used in an amount of 0.8 to 1.2 moles compared to the compound (4).

Step 2 is carried out without solvent or in a solvent. Reaction 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, dibutyl ether, and tert-butyl. Ether solvents such as methyl ether, alcohol solvents such as methanol, ethanol, iso-propanol and ethylene glycol, amine solvents such as pyridine and triethylamine, nitrile solvents such as acetonitrile and benzonitrile, methylene chloride, 1,2- A halogen-based solvent such as dichloroethane, an aprotic polar solvent such as N, N-dimethylformamide, dimethyl sulfoxide, or a suitable mixed solvent of the above-mentioned solvents can be used. In particular, an aliphatic hydrocarbon solvent or an ether solvent solvent It is preferable to carry out in the inside.
The amount of solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate.

  The temperature in step 2 is preferably from -100 ° C to 250 ° C, particularly preferably from -75 ° C to 0 ° C.

  The reaction time in step 2 is preferably 0.5 to 48 hours, and particularly preferably 0.5 to 8 hours.

Next, production method 2 will be described.
[Production Method 2] A method for producing compound (1) by reacting compound (2) with compound (5).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
^{CHX 2 = CH-A 5 -} (Z 4 -A 6) p - (Z 5 -A 7) q - (Z 6 -A 8) r -R 2 (5)
Each symbol in the above formulas is as described above in formula (1), and X ¹ and X ² are each independently a chlorine atom, a bromine atom or an iodine atom.

The method for obtaining compound (2) is as described in Production Method 1.
Compound (5) can also be obtained based on a known method, for example, according to the method of the following literature.
Synlett 1999, No. 8, 1268-1270, Journal of American Chemical Society 1986, 108, 7408-7410, Journal of American Chemical Society 1973, 95, 6456-5457, Journal of American Chemical Society 1973, 95, 5786-5787 and Organic Letters 2008,10,5485-5488.
For example, when the compound (5) is the following compound (5-1), the following compound (8) is reacted with a chromium compound and iodoform, or the following compound (9) is hydroborated and then reacted with iodine. Can be obtained.
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -Ph-CHO (8)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -Ph-C≡CH (9)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n - (A 3 -Z 3) o -Ph-CH = CHI (5-1)

  In production method 2, compound (5) is usually used in an amount of 0.5 to 2 mol per 1 mol of compound (2).

  The reaction between the compound (2) and the compound (5) is performed using a metal reagent. As the metal reagent, aluminum, lead, copper, zinc, palladium tetrakistriphenylphosphine, magnesium or the like can be used. In particular, it is preferable to use copper.

Production method 2 is carried out without solvent or in a solvent. Reaction 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, dibutyl ether, and tert-butyl. Ether solvents such as methyl ether, amine solvents such as pyridine and triethylamine, nitrile solvents such as acetonitrile and benzonitrile, halogen solvents such as methylene chloride and 1,2-dichloroethane, N, N-dimethylformamide, dimethyl sulfoxide An aprotic polar solvent such as the above or a suitable mixed solvent of the above solvents can be used, but it is particularly preferable to carry out in N, N-dimethylformamide or dimethyl sulfoxide.
The amount of solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate.

  The reaction temperature of production method 2 is preferably from -100 ° C to 250 ° C, particularly preferably from 80 ° C to 160 ° C.

  The reaction time is preferably 0.5 to 48 hours, and particularly preferably 2 to 16 hours.

  Since the compound (1) of the present invention has the characteristics of low viscosity, high clearing point, and chemical stability, at least one of them is mixed with other liquid crystal compounds and / or non-liquid crystal compounds. A liquid crystal composition satisfying conditions such as high-speed response and a wide operating temperature range can be prepared.

  The compound other than the compound (1) in the liquid crystal composition varies depending on the use of the liquid crystal composition, required performance, etc., but usually the main component is a liquid crystal compound and a compound having a similar structure to the liquid crystal compound. It is preferable to add other compounds as required.

Specific examples of other compounds include components that improve dielectric anisotropy, components that exhibit liquid crystallinity at high temperatures, low viscosity components, components that adjust refractive index anisotropy, components that impart cholesteric properties, two colors Components exhibiting electrical properties, components imparting electrical conductivity, and the like. Examples of other compounds that can be included in the liquid crystal composition include the following specific examples. R ³ and R ⁴ in the following formulas may be the same or different and each represents a group such as an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a halogen atom, or a cyano group, and —Ph -And -Cy- have the same meaning as described above.

R ³ -Cy-Cy-R ⁴
R ³ -Cy-Ph-R ⁴
R ³ -Ph-Ph-R ⁴
R ³ —Ph—C≡C—Ph—R ⁴
R ³ -Cy-COO-Ph-R ⁴
R ³ -Ph-COO-Ph-R ⁴
R ³ —Cy—CH═CH—Ph—R ⁴
R ³ —Cy—CH ₂ CH ₂ —Ph—R ⁴
R ³ —Ph—CH ₂ CH ₂ —Ph—R ⁴
R ³ -Cy-Cy-Ph-R ⁴
R ³ -Cy-Ph-Ph-R ⁴
R ³ -Cy-Ph-C≡C-Ph-R ⁴
R ³ -Ph-Ph-Ph-R ⁴
R ³ -Cy-Ph-Ph-Cy-R ⁴
R ³ -Ph-Ph-C≡C-Ph-R ⁴
R ³ -Cy-COO-Ph-Ph-R ⁴
R ³ -Cy-Ph-COO-Ph-R ⁴
R ³ -Cy-COO-Ph-COO-Ph-R ⁴
R ³ —Ph—COO—Ph—COO—Ph—R ⁴
R ³ —Ph—COO—Ph—OCO—Ph—R ⁴

  Moreover, as another compound included in a liquid-crystal composition, it is not limited to the said compound. For example, the ring structure or terminal group hydrogen atom of the compound may be substituted with a halogen atom, a cyano group, or a methyl group, and the ring structure or terminal group hydrogen atom of the compound is a cyclohexane ring. , A benzene ring, a pyrimidine ring, or another 6-membered ring such as a dioxane ring or a 5-membered ring. Moreover, you may change the coupling group which exists between a ring into another coupling group. These substitutions or changes may be appropriately selected according to the target performance.

  A liquid crystal composition containing the compound (1) of the present invention is sandwiched between substrates with electrodes, for example, by being injected into a liquid crystal cell to constitute a liquid crystal electro-optical element. As a typical liquid crystal cell, there is a TN liquid crystal electro-optical element. Note that the expression “liquid crystal electro-optical element” is used here for the purpose of clarifying that the liquid crystal electro-optical element can be used for, for example, a dimming window, an optical shutter, and a polarization exchange element other than the display application.

  The above liquid crystal electro-optical elements are TN mode, STN mode, ECB mode, VA mode, guest-host (GH) mode, dynamic scattering mode, phase change mode, DAP mode, dual frequency drive mode, ferroelectric liquid crystal display mode. It can be used in various modes. As a drive mode, passive drive and active drive can be used.

Hereinafter, a specific example of the configuration and manufacturing method of the liquid crystal electro-optical element will be described. If necessary, an undercoat layer such as SiO ₂ or Al ₂ O ₃ or a color filter layer is formed on a substrate such as plastic or glass, and electrodes such as In ₂ O ₃ —SnO ₂ (ITO) or SnO ₂ are formed. After providing and patterning, if necessary, an overcoat layer of polyimide, polyamide, SiO ₂ , Al ₂ O ₃ or the like is formed, aligned, printed with a sealing material, and the electrode surfaces are opposed to each other. Disposed to seal the periphery and harden the sealing material to form an empty cell.

  A composition containing the compound of the present invention is injected into this 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., and non-glare processing. To obtain a liquid crystal electro-optical element.

  Note that the above description describes the basic configuration and manufacturing method of the liquid crystal 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 used. In particular, the composition of the present invention is also suitable for active matrix devices such as TFT and MIM.

  Further, modes other than the TN type described above, that is, a super twist nematic (STN) type liquid crystal element having a high twist angle, a guest-host (GH) type liquid crystal element using a pleochroic dye, and a liquid crystal with a horizontal electric field. In-plane switching (IPS) type liquid crystal element that drives molecules parallel to the substrate, VA type liquid crystal element that aligns liquid crystal molecules vertically with respect to the substrate, ferroelectric liquid crystal element, etc. I can do it. 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 specifically described with reference to examples. However, the examples shown below are intended to illustrate the present invention, and the present invention is not limited thereto.

Example 1

12.79 g of compound (2A) synthesized according to the description of JP-A No. 2002-128776, 7.40 g of compound (3A) synthesized according to the description of JP-A No. 8-170078 and benzoyl peroxide (about 25% water) Wet product) 1.26 g was stirred at 90 ° C. for 12 hours. The reaction was quenched by adding 20 ml of water and 20 ml of hexane, and the organic layer was washed with 5% aqueous sodium bicarbonate solution and water, and then concentrated to obtain 20.60 g of compound (4A) as a crude product. The product was directly used in the next step without further purification.

After cooling 24.61 g of the compound (4A) obtained above and 120 ml of THF to −70 ° C., 9.88 g of diazabicycloundecene was added dropwise and stirred for 2 hours. Further, 130 ml of an approximately 0.5 [mol / l] toluene solution of potassium hexamethyldisilazide was dropped, and the mixture was gradually warmed to room temperature and stirred overnight. After quenching with 100 ml of 10% aqueous ammonium chloride solution, hexane was added, washed with 5% hydrochloric acid, 5% aqueous sodium bicarbonate solution and water, and concentrated. The obtained crude product was recrystallized using silica chromatography (developing solvent: hexane) and a mixed solvent of ethanol and hexane to obtain 1.74 g of compound (1A).

¹⁹ F-NMR (282.6 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −110.60 (m, F, CF ₂ ), −119.34 (m, 2F, CF ₂ )
¹ H-NMR (282.6 MHz, solvent CDCl ₃ , standard: SiMe ₄ ) δ (ppm): 6.20 (m, 1H, vinyl), 5.54 (m, 1H, vinyl), 2.0-0 .8 (m, 34H)
GC-MS M ⁺ = 376
Phase series: C65.3N77.3I (C: crystal, N: nematic phase, I: isotropic phase)

  Using a composition obtained by mixing 10% by mass of the compound (1A) and 90% by mass of a liquid crystal composition “ZLI-1565” manufactured by Merck, the refractive index anisotropy (Δn) at 25 ° C. The value obtained by extrapolation was 0.067.

(Example 2)

Under a nitrogen atmosphere, 20.17 g of the compound (2B) synthesized according to the description of the above-mentioned Journal of Fluorine Chemistry, 11.45 g of the compound (3A) synthesized in the same manner as in Example 1, benzoyl peroxide (about 25% wet with water) Product) 1.86 g was heated and stirred at 90 ° C. for 8 hours. Hexane and water were added to the resulting crude oil, and the organic layer was washed with 5% aqueous sodium bicarbonate solution and water, and concentrated to obtain 30.63 g of compound (4B) as a crude product. The product was directly used in the next step without further purification.

After cooling 30.63 g of compound (4B) and 150 ml of THF to −70 ° C., 12.95 g of diazabicycloundecene was added dropwise, and 160 ml of about 0.5 mol / l toluene solution of potassium hexamethyldisilazide was further added dropwise. The mixture was gradually warmed to room temperature and stirred overnight. After quenching with 100 ml of 10% aqueous ammonium chloride solution, hexane was added, washed with 5% hydrochloric acid, 5% aqueous sodium bicarbonate solution and water, and concentrated. The obtained crude product was recrystallized using silica chromatography (developing solvent: hexane) and a mixed solvent of ethanol and hexane to obtain 2.45 g of compound (1B).

¹⁹ F-NMR (282.6 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −112.34 (m, 2F, CF ₂ ), −112.72 (m, 2F, CF ₂ )
¹ H-NMR (282.6 MHz, solvent CDCl ₃ , standard: SiMe ₄ ) δ (ppm): 7.36 (d, 2H, Ar), 7.16 (d, 2H, Ar), 6.05 (m , 2H, vinyl), 5.47 ( m, 2H, vinyl), 2.55 (t, 2H, CH 2), 1.69-0.78 (m, 22H)
GC-MS M ⁺ = 370
Phase sequence: C17.6I (C: crystal, I: isotropic phase)

  Using a composition obtained by mixing 10% by mass of the compound (1B) and 90% by mass of a liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc., the refractive index anisotropy (Δn) at 25 ° C. The value obtained by extrapolation was 0.055.

(Synthesis Example 1)

Under a nitrogen stream, 18.65 g of catechol and 90 ml of THF were ice-cooled, and 168 ml of a THF solution of 0.9 [mol / l] borane-tetrahydrofuran complex was dropped, and the temperature was gradually raised to room temperature. 20.05 g of (4-propylphenyl) acetylene was added dropwise and stirred at 40 ° C. for 3 hours. After cooling with ice, 190 ml of water was added dropwise and stirred overnight. Extraction and concentration with toluene gave 35.71 g of a crude product of a boric acid derivative. The product was directly used in the next step without purification.
35.71 g of the boric acid derivative obtained above and 100 ml of ether were cooled, and 12 g of sodium hydroxide and 100 ml of water were added dropwise. Furthermore, 42.60 g of iodine and 300 ml of ether were added dropwise and stirred for 1 hour. After quenching with 10% sodium thiosulfate, filtration, the organic layer was extracted with toluene, washed with 5% aqueous sodium bicarbonate and water, and concentrated. The resulting crude product was purified by silica chromatography (developing solvent: hexane) to obtain 24.53 g of compound (5C).

(Example 3)

In a nitrogen stream, 28.05 g of Compound (2B), 32.41 g of Compound (5C) obtained in the same manner as in Synthesis Example 1, 10.81 g of copper powder and 200 ml of dimethyl sulfoxide were heated at 130 ° C. for 5 hours, and then 140 Heating was performed at 0 ° C. for 8 hours. The resulting crude oil was cooled to room temperature and 100 ml of water was added dropwise. The organic layer was extracted with hexane, washed with water until neutral, and concentrated. The obtained crude product was purified by silica chromatography (developing solvent: hexane) and then recrystallized from hexane to obtain 4.90 g of compound (1C).

¹⁹ F-NMR (282.6 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −11.37 (m, 2F, CF ₂ ), −118.94 (m, 2F, CF ₂ )
¹ H-NMR (282.6 MHz, solvent CDCl ₃ , standard: SiMe ₄ ) δ (ppm): 7.37 (d, 2H, Ar), 7.17 (d, 2H, Ar), 7.03 (d , 1H, vinyl), 6.19 ( m, 1H, vinyl), 2.59 (t, 2H, CH 2), 2.0-1.0 (m, 22H)
GC-MS M ⁺ = 364
Phase sequence: C39.4 ° C. I (C: crystal, I: isotropic phase)

  Using a composition obtained by mixing 10% by mass of the compound (1C) and 90% by mass of a liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc., refractive index anisotropy (Δn) at 25 ° C. The value obtained by extrapolation was 0.100.

Example 4

Under a nitrogen stream, 28.05 g of the compound (2A), 20.08 g of the compound (5C) obtained in the same manner as in Synthesis Example 1, 11.02 g of copper powder and 200 ml of dimethyl sulfoxide were obtained at 130 ° C. for 2 hours and a half and 140 ° C. For 6 hours. The resulting crude oil was cooled to room temperature and 100 ml of water was added dropwise. The organic layer was extracted with hexane, washed with 5% aqueous sodium bicarbonate solution and water, and concentrated. The obtained crude product was purified by silica chromatography (developing solvent: hexane) and then recrystallized from hexane to obtain 8.34 g of Compound (1D).

¹⁹ F-NMR (282.6 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −11.33 (m, 2F, CF ₂ ), 118.84 (m, 2F, CF ₂ )
¹ H-NMR (282.6 MHz, solvent CDCl ₃ , standard: SiMe ₄ ) δ (ppm): 7.37 (d, 2H, Ar), 7.17 (d, 2H, Ar), 7.02 (m , 1H, vinyl), 6.19 (m, 1H, vinyl), 2.59 (t, 2H, benzyl), 2.6-0.85 (m, 22H)
GC-MS M ⁺ = 360
Phase sequence: C (43.1 N) 45.8 ° C. I (C: crystal, N: nematic phase, I: isotropic phase)

  Using a composition obtained by mixing 10% by mass of the compound (1D) and 90% by mass of a liquid crystal composition “ZLI-1565” manufactured by Merck, the refractive index anisotropy (Δn) at 25 ° C. The value obtained by extrapolation was 0.122.

  Further, the following physical properties were measured using Merck liquid crystal composition ZLI-1565 as the mother liquid crystal. Compound C1 and Compound C2 were synthesized with reference to the method described in JP-A-10-7598.

[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). As a sample, a liquid crystal composition composed of 90% by mass of the mother liquid crystal and 10% by mass of the compound (1A) and a liquid crystal composition composed of 90% by mass of the mother liquid crystal and 10% by mass of the compound (C1) were adjusted to obtain the clearing point. . The results are shown in Table 1.

[Bulk viscosity]
A liquid crystal composition consisting of 90% by mass of the mother liquid crystal and 10% by mass of the compound (1A) was prepared, measured at 25 ° C. using a shear viscometer, and calculated by extrapolation. A liquid crystal composition comprising 90% by mass of the base liquid crystal and 10% by mass of the comparative compound (C2) was prepared, and similarly measured and calculated. The results are shown in Table 2.

Based on the examples and synthesis examples, the following compound can be produced as compound (1).
In the formulas shown below, -Ph- and -Cy- are the same as described above, and the other symbols have the following meanings.
-Ph (3F)-: 3-fluoro-1,4-phenylene group.
-Ph (3F, 5F)-: 3,5-difluoro-1,4-phenylene group.
-Ph (2F, 3F)-: 2,3-difluoro-1,4-phenylene group.

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Cy-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Cy-C 2 H 5
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Cy-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Cy-C 5 H 11
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-C 4 H 9
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-C 5 H 11
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Cy-C 5 H 11
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-OCH 3

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Ph-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-C 2 H 5
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-C 4 H 9
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-OCH 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-CF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-OCF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph (3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph (2F, 3F) -F

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Ph-Ph-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-C 2 H 5
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-C 4 H 9
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-OCH 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-CF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-OCF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph (3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph (2F, 3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph (3F, 5F) -Ph (3F, 5F) -F

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Cy-Ph-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-C 2 H 5
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-C 4 H 9
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-OCH 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-CF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-OCF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph-F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph (3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Cy-Ph (2F, 3F) -F

_{CH 3 -Cy-Cy-CF 2} CF 2 CH = CH-Cy-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 2 H 5
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 5 H 11
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 2 H 5
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 4 H 9
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 5 H 11
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 2 H 5
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 3 H 7
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-C 5 H 11
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-OCH 3

_{CH 3 -Cy-Cy-CF 2} CF 2 CH = CH-Ph-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-C 2 H 5
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-C 4 H 9
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-OCH 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-CF 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-OCF 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph (3F) -F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph (2F, 3F) -F

_{CH 3 -Cy-Cy-CF 2} CF 2 CH = CH-Cy-Cy-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 2 H 5
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 5 H 11
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 2 H 5
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 4 H 9
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 5 H 11
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 2 H 5
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 3 H 7
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-C 5 H 11
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-OCH 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-CF 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Cy-Cy-OCF 3

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 2 H 5
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 4 H 9
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-OCH 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-CF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-OCF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph (3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph (2F, 3F) -F

_{CH 3 -Cy-Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 2 H 5 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-C 2 H 5
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-C 4 H 9
_{C 5 H 11 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-OCH 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-CF 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-OCF 3
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph-F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph (3F) -F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-Cy-} CF 2 CF 2 CH = CH-Ph-Ph-Ph (2F, 3F) -F

_{CH 3 -Cy-CF 2 CF 2} CH = CH-Ph-Ph-Ph-Ph-C 3 H 7
_{C 2 H 5 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-C 2 H 5
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-C 4 H 9
_{C 5 H 11 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-C 3 H 7
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-OCH 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-CF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-OCF 3
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph-F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph (3F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph (3F, 5F) -F
_{C 3 H 7 -Cy-CF 2} CF 2 CH = CH-Ph-Ph-Ph-Ph (2F, 3F) -F

Claims (6)

A fluorine-containing compound represented by the following formula (1).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH = CH-A ^5- (Z ⁴ -A ⁶ _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (1)
The symbols in the above formula have the following meanings.
R ¹ and R ² : independently of each other, a hydrogen atom, a halogen atom, or a monovalent acyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms. However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and the bond terminal of the aliphatic hydrocarbon group or between carbon-carbon atoms in the aliphatic hydrocarbon group -O- or -S- may be inserted.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ : independently of each other, a trans-1,4-cyclohexylene group, a 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 -A diyl 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. Two —CH ₂ — groups may be substituted with —O— or —S—.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ : independently of each other, a single bond, —O—, —S—, —COO— or a divalent acyclic ring having 1 to 4 carbon atoms Formula aliphatic hydrocarbon group. However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and the bond terminal of the aliphatic hydrocarbon group or between carbon-carbon atoms in the aliphatic hydrocarbon group -O- or -S- may be inserted.
m, n, o, p, q, r: 0 or 1 independently of each other. However, m + n + o + p + q + r is 3 or less. The fluorine-containing liquid crystal compound according to claim 1, wherein the compound is represented by the following formula (1-1).
^{R 11 - (A 11 -Z 11} ) m - (A 21 -Z 21) n - (A 31 -Z 31) o -A 41 -CF 2 CF 2 CH = CH-A 51 - (Z 41 -A 61 _p- (Z ⁵¹ -A ⁷¹ ) _q- (Z ⁶¹ -A ⁸¹ ) _r -R ²¹ (1-1)
The symbols in the above formula have the following meanings.
R ¹¹ , R ²¹ : independently of each other, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with fluorine atoms, and —O— or —S— may be inserted between carbon-carbon atoms in the group or at the bond terminal of the group. .
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ , A ⁷¹ , A ⁸¹ : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group. However, one or more hydrogen atoms present in the 1,4-phenylene group may be substituted with fluorine atoms.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁵¹ , Z ⁶¹ : independently of each other, a single bond, —O—, —S—, or an alkylene group having 1 to 4 carbon atoms. However, one or more hydrogen atoms in the group may be substituted with a halogen atom, and —O— or —S— is inserted between carbon-carbon atoms in the group or at the bond terminal of the group. It may be.
m, n, o, p, q and r have the same meaning as described above. The manufacturing method of the compound represented by Formula (1) of Claim 1 including the following process 1 and process 2.
Step 1: A step of producing a compound represented by the following formula (4) by an addition reaction between the compound represented by the following formula (2) and the compound represented by the following formula (3).
Step 2: a step of dehydrohalogenating a compound represented by the following formula (4) in the presence of a base to obtain a compound represented by the following formula (1).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH = CH-A ^5- (Z ⁴ -A ⁶ _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (1)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
^{_{CH 2 = CH-A 5 -}} (Z 4 -A 6) p - (Z 5 -A 7) q - (Z 6 -A 8) r -R 2 (3)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH ₂ CHX ¹ -A ^5- (Z ⁴ -A ⁶ ) _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (4)
In the above formulas, X ¹ is a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , m, n, o, p, q, r have the same meaning as each symbol in claim 1. The manufacturing method of the compound represented by Formula (1) of Claim 1 by making the compound represented by the following Formula (2) react with the compound represented by the following Formula (5).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ X ¹ (2)
↓ CHX ² = CH-A ^5- (Z ⁴ -A ⁶ ) _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (5)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n- (A ³ -Z ³ ) _o -A ⁴ -CF ₂ CF ₂ CH = CH-A ^5- (Z ⁴ -A ⁶ _p- (Z ⁵ -A ⁷ ) _q- (Z ⁶ -A ⁸ ) _r -R ² (1)
In the above formulas, X ¹ and X ² are each independently a chlorine atom, bromine atom or iodine atom, and R ¹ , R ² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , m, n, o, p, q, r have the same meaning as each symbol in claim 1.   A liquid crystal composition containing the fluorine-containing compound according to claim 1.   6. A liquid crystal electro-optical element comprising the liquid crystal composition according to claim 5 sandwiched between substrates with electrodes.