JP2008019225A - Fluorine-containing compound, method for producing fluorine-containing compound and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorine-containing compound useful for a functional material such as a liquid crystal material; to provide a composition containing the compound, and a liquid crystal electro-optical element containing the composition; and to provide an industrially applicable method for producing the compound. <P>SOLUTION: The fluorine-containing compound is represented by R<SP>1</SP>-(A<SP>1</SP>-Z<SP>1</SP>)<SB>m</SB>-(A<SP>2</SP>-Z<SP>2</SP>)<SB>n</SB>-A<SP>3</SP>-(CH<SB>2</SB>)<SB>p</SB>-CF=CF-(CH<SB>2</SB>)<SB>q</SB>-A<SP>4</SP>-(Z<SP>3</SP>-A<SP>5</SP>)<SB>r</SB>-(Z<SP>4</SP>-A<SP>6</SP>)<SB>s</SB>-R<SP>2</SP>(1) (wherein, R<SP>1</SP>and R<SP>2</SP>are mutually independently a hydrogen atom, a halogen atom or a 1-10C monovalent aliphatic hydrocarbon group; A<SP>1</SP>to A<SP>6</SP>are mutually independently a phenylene group or a cyclohexylene group; Z<SP>1</SP>to Z<SP>4</SP>are mutually independently a single bond, -O-, -S- or a 1-4C divalent aliphatic hydrocarbon group; m, n, r and s are mutually independently 0 or 1; p and q are mutually independently an integer of 0-3; with the proviso that p+q is ≥1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel fluorine-containing 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.

  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

  An object of the present invention is to provide a novel fluorine-containing compound useful as a functional material such 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 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 - (CH 2) p -CF = CF- (CH 2) q -A 4 - (Z 3 -A 5) _r- (Z ⁴ -A ⁶ ) _s -R ² (1)
(However, the symbols in the formula have the following meanings.
R ¹ and R ² : independently of each other, a hydrogen atom, a halogen atom, or a monovalent 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 In addition, an etheric oxygen atom or a thioetheric sulfur atom may be inserted.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ : independently of one another, a phenylene group or a cyclohexylene group. However, one or more hydrogen atoms in the groups A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ may be substituted with a halogen atom, and one or two existing in the group One —CH═ may be substituted with a nitrogen atom, and one or two —CH ₂ — present in the group may be substituted with an etheric oxygen atom or a thioetheric sulfur atom. However, two —CH ₂ — are not continuously substituted by an etheric oxygen atom or a thioetheric sulfur atom.
Z ¹ , Z ² , Z ³ , Z ⁴ : each independently a single bond, —O—, —S—, or a divalent aliphatic hydrocarbon group having 1 to 4 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 In addition, an etheric oxygen atom or a thioetheric sulfur atom may be inserted.
m, n, r, s: 0 or 1 independently of each other.
p, q: An integer of 0 to 3 independently of each other. However, p + q is 1 or more. )

  In the compound (1), m + n + r + s is preferably 2 or less.

  In the compound (1), both p and q are preferably 1.

In the compound (1), it is also preferred that Z ¹ , Z ² , Z ³ and Z ⁴ are all single bonds.

In the compound (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ may be independently 1,4-cyclohexylene group or 1,4-phenylene group. preferable. One or more hydrogen atoms present in the 1,4-phenylene group may be substituted with a fluorine atom.

The present invention also provides a process for producing compound (1).
Compound (2) is metalated, this is reacted with tetrafluoroethylene to synthesize compound (3), and compound (4) is similarly reacted with compound (3) to react with compound (3). 1) is manufactured.
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -X (2)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -CF = CF ₂ (3)
^{_{X- (CH 2) q -A 4}} - (Z 3 -A 5) r - (Z 4 -A 6) s -R 2 (4)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n -A 3 - (CH 2) p -CF = CF- (CH 2) q -A 4 - (Z 3 -A 5) _r- (Z ⁴ -A ⁶ ) _s -R ² (1)
(Wherein, X is chlorine atom, a bromine atom or an iodine ^{atom, R 1, R 2, A} 1, A 2, A 3, A 4, A 5, A 6, Z 1, Z 2, Z 3, Z ⁴ , m, n, p, q, r, and s 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.

  The compound of the present invention can be synthesized easily and simply industrially, and can be used for liquid crystal compositions and the like. Further, from the structure of the compound of the present invention, it can be expected that effects such as a decrease in viscosity, optimization of elastic constants, and improvement of light resistance can be achieved.

In the compound (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a monovalent 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, an etheric oxygen atom or a thioetheric sulfur atom 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 an etheric oxygen atom or a thioetheric sulfur atom may be simultaneously performed on the same aliphatic hydrocarbon group.

  Examples of the monovalent 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 an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon atoms in these groups include alkoxyalkyl groups and alkylthioalkyl groups. Examples of the group in which an etheric oxygen atom or a thioetheric sulfur atom is inserted at the bond terminal of the group include an alkoxy group and an alkylthio group. Further, examples of the group in which substitution with a halogen atom and insertion of an etheric oxygen atom are performed on the same aliphatic hydrocarbon group include a fluoroalkoxy group. These groups may be either linear or branched, but are preferably linear.

  As a C1-C10 alkyl group, a C1-C5 alkyl group is preferable, and an ethyl group, a propyl group, or a pentyl group is especially preferable. As an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable. The fluoroalkyl group having 1 to 10 carbon atoms is preferably a fluoroalkyl group having 1 to 5 carbon atoms, and particularly preferably a trifluoromethyl group. The fluoroalkoxy group having 1 to 10 carbon atoms is preferably a fluoroalkoxy group having 1 to 5 carbon atoms, and particularly preferably a trifluoromethoxy group. As the halogen atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable.

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 an etheric oxygen atom or a thioetheric sulfur at a bond between the carbon-carbon atoms or the group in the group An atom may be inserted.
In particular, a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, an alkoxy group, a fluoroalkyl group, or a fluoroalkoxy group is preferable. Further, a fluorine atom, a linear alkyl group having 1 to 5 carbon atoms, an alkoxy group, a fluoroalkyl group, or a fluoroalkoxy group is more preferable.

In the compound (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a phenylene group or a cyclohexylene 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 an etheric oxygen atom or a thioetheric sulfur atom. However, two —CH ₂ — are not continuously substituted by an etheric oxygen atom or a thioetheric sulfur atom.

Since A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ have a linear structure and are easy to use for liquid crystals, 1,4-cyclohexylene group and 1,4-phenylene group are preferable. From the viewpoint of compatibility and dielectric anisotropy when used for liquid crystals, it is also preferred that the 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 and Z ⁴ are each independently a single bond, —O—, —S—, or a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. However, one or more hydrogen atoms in the aliphatic hydrocarbon group may be substituted with a halogen atom, and an ether group may be bonded between carbon-carbon atoms in the aliphatic hydrocarbon group or in the aliphatic hydrocarbon group. Oxygen atoms or thioetheric sulfur atoms may be inserted. Note that the substitution with a halogen atom and the insertion of an etheric oxygen atom or a thioetheric sulfur atom 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 Z ¹ is a single bond and n is 0, A ¹ and A ³ are directly bonded. When 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 and Z ⁴ .

  Examples of the divalent 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 group in which one or more hydrogen atoms in these groups are substituted with a halogen atom include a fluoroalkylene group, a chloroalkylene group, and a fluoroalkenylene group. Further, groups in which an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon atoms in these groups or at the bond terminal of the group include oxyalkylene groups, alkyloxyalkylene groups, thioalkylene groups, oxyalkylene groups, A fluoroalkylene group or a thiofluoroalkylene group can be mentioned.

The alkylene group having 1 to 4 carbon _{atoms, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, or _{-CH 2 CH 2 CH 2 CH 2} - . In particular -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—, or — CH ₂ —CH═CH—CH ₂ — can be mentioned, and —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—, or — CH ₂ —C≡C—CH ₂ — can be mentioned, and —C≡C— is particularly preferable. Further, double bonds and triple bonds may be mixed as in —CH═CH—C≡C—.

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 —, or —CF═CF—C≡C— can be mentioned, and —CF ₂ CF ₂ — or —CF═CF— is particularly preferable.

Examples of the oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group, alkyloxyalkylene group, oxyfluoroalkylene group, and 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-, or -CF ₂ S- can be cited, -OCF ₂ - or -CF ₂ O-are preferred .

When Z ¹ , Z ² , Z ³ and Z ⁴ are bonded to a phenylene group, it is preferable that the bonded portion has a structure having no unsaturated bond such as a double bond from the viewpoint of stability of the compound.

Z ¹ , Z ² , Z ³ and Z ⁴ are preferably a single bond, —O—, —S—, or an alkylene group having 1 to 4 carbon atoms from the viewpoint of stability of the compound and ease of synthesis. One or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom, and an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon atoms in the alkylene group or at the bond terminal of the group. May be. 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, r and s are each independently 0 or 1. Since the viscosity is not so high, m + n + r + s is preferably 2 or less.

  In the compound (1), p and q are each independently an integer of 0 to 3. However, p + q is 1 or more. It is preferable that p and q are both 1.

  As the compound (1), the compound (1-1) is preferable, the compound (1-2) is more preferable, and the compound (1-3) is particularly preferable.

^{R 11 - (A 11 -Z 11} ) m - (A 21 -Z 21) n -A 31 - (CH 2) p -CF = CF- (CH 2) q -A 41 - (Z 31 -A 51) _r- (Z ⁴¹ -A ⁶¹ ) _s -R ²¹ (1-1)
(However, the symbols in the formula have the following meanings.
R ¹¹ and R ^{21 are} each independently 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 an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon atoms in the group or at the bond terminal of the group. Also good.
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , A ⁶¹ : each independently 1,4-cyclohexylene group or 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 : each independently 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 an etheric oxygen atom or a thioetheric sulfur atom is present between carbon-carbon atoms in the group or at the bond terminal of the group. It may be inserted.
m, n, p, q, r, and s have the same meaning as described above. )

^{R 12 - (A 11 -Z 12} ) m - (A 21 -Z 22) n -A 31 - (CH 2) p -CF = CF- (CH 2) q -A 41 - (Z 32 -A 51) _r- (Z ⁴² -A ⁶¹ ) _s -R ²² (1-2)
(However, the symbols in the formula have the following meanings.
R ¹² and R ^{22 are} each independently 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 : 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 , m, n, p, q, r, and s have the same meaning as described above. )

_{^{R 13 - (A 11) m}} -A 31 - (CH 2) p -CF = CF- (CH 2) q -A 41 - (A 61) s -R 23 (1-3)
(However, the symbols in the formula have the following meanings.
R ¹³ and R ^{23 are} 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 ³¹ , A ⁴¹ , A ⁶¹ , m, p, q, and s have the same meaning as described above. )

  Specific examples of the compound (1) include the following compounds.

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

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

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

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

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

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

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

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

However, the symbols in the formulas have the following meanings.
Cy: trans-1,4-cyclohexylene group.
Ph: 1,4-phenylene group.
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.

Compound (1) of the present invention can be synthesized by the following method. The symbols in the formula have the same meaning as described above.
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -X (2)
↓
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -CF = CF ₂ (3)
_{↓ X- (CH 2) q -A} 4 - (Z 3 -A 5) r - (Z 4 -A 6) s -R 2 (4)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n -A 3 - (CH 2) p -CF = CF- (CH 2) q -A 4 - (Z 3 -A 5) _r- (Z ⁴ -A ⁶ ) _s -R ² (1)

  Compound (2) is metalized and then reacted with tetrafluoroethylene to synthesize compound (3). In addition, compound (4) is similarly metallized, and compound (1) can be obtained by reacting this with compound (3). Examples of the metalation of compound (2) or compound (4) include a method of lithiation with metallic lithium or the like, and a method of using a Grignard reagent by reaction with metallic magnesium.

  When lithiation is performed using metallic lithium, lithiation may be performed in the presence of an electron transfer agent. As the electron transfer agent, a compound having two or more aromatic rings or a condensed ring is used. Specific examples include naphthalene, biphenyl, 2,6-di-tert-butylnaphthalene, 2,7-di-tert-butylnaphthalene, 4,4′-di-tert-butylbiphenyl, and anthracene. Are naphthalene, biphenyl, 4,4′-di-tert-butylbiphenyl. The amount of the electron transfer agent used is 0.01 to 4 times mol, preferably 0.1 to 2.5 times mol with respect to compound (2) or compound (4).

  The amount of metallic lithium used is 2 to 5 times, preferably 2 to 3 times the mol of the compound (2) or compound (4). When the Grignard reagent is prepared by reaction with metallic magnesium, the amount of metallic magnesium used is 1 to 5 moles, preferably 1 to 1.5 moles.

  The metalation reaction is carried out in a solvent. Reaction solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, tetrahydrofuran, diethyl ether, dibutyl ether, t-butyl methyl ether, etc. Ether solvents, petroleum ethers, or a suitable mixed solvent of the above solvents can be used, and ether solvents or a mixed solvent of an ether solvent and an aliphatic hydrocarbon solvent is particularly preferable. The amount of solvent varies greatly depending on the scale of synthesis, and can be changed as appropriate. For example, in the case of a lab scale, it is preferable to use a volume (mL) of 0.1 to 10,000 times with respect to 1 mol of compound (2) or compound (4), and a volume of 0.5 to 3000 times ( More preferably, mL) is used.

  The reaction temperature of the metalation reaction is preferably from -100 ° C to 100 ° C, particularly preferably from -80 ° C to 70 ° C.

  The reaction time of the metalation reaction is preferably 0.5 hours to 48 hours, particularly preferably 0.5 hours to 8 hours.

  After the metallation of the compound (2), the compound (3) can be obtained by continuously reacting with tetrafluoroethylene without isolation. That is, it is carried out by passing tetrafluoroethylene gas through the reaction liquid after completion of metalation. The amount of tetrafluoroethylene to be used is 1 to 10 times mol, preferably 1 to 3 times mol, of compound (2). If desired, tetrafluoroethylene may be diluted with an inert gas such as nitrogen or argon. Although the dilution ratio is arbitrary, the ratio of tetrafluoroethylene is preferably 30 to 70% from the viewpoint of safety and efficiency.

  In the reaction between the metallized product and tetrafluoroethylene, the reaction temperature between the lithiated product and tetrafluoroethylene is preferably -100 ° C to 25 ° C, and particularly preferably -80 ° C to 0 ° C. The reaction temperature of the Grignard reagent and tetrafluoroethylene is preferably -100 ° C to 80 ° C, particularly preferably 0 ° C to 50 ° C.

  In the reaction between the metalated product and tetrafluoroethylene, the reaction time is preferably 0.5 to 48 hours, particularly preferably 0.5 to 24 hours.

  After the reaction, the compound (3) can be obtained by carrying out usual post-treatment operations and purification operations.

  Compound (1) can be obtained by reacting compound (3) with the metalated product of compound (4). To this, the compound (3) may be added to the compound (4) metallation reaction solution prepared separately as described above, or the compound (4) metalation reaction solution prepared separately to the compound (3). May be added.

  Compound (3) may be diluted with a solvent in advance. Diluting 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, dibutyl ether, t-butyl methyl ether, etc. Ether solvents, petroleum ethers, or a suitable mixed solvent of the above solvents can be used, and ether solvents or a mixed solvent of an ether solvent and an aliphatic hydrocarbon solvent is particularly preferable. The amount of diluting solvent varies greatly depending on the scale of synthesis and can be changed as appropriate. For example, in the case of a lab scale, it is preferable to use a volume (mL) of 0.1 to 2000 times, and a volume (mL) of 0.5 to 1000 times with respect to 1 mol of compound (3). Is more preferable.

  The reaction temperature is preferably from -100 ° C to 100 ° C. In the case of a lithiated compound (4), -80 ° C to 25 ° C is particularly preferable, and in the case of the Grignard reagent of compound (4), particularly from 0 ° C to 70 ° C. is preferred.

  The reaction time is preferably 0.5 hours to 48 hours, particularly preferably 0.5 hours to 24 hours.

  After the reaction, a new fluorine-containing compound represented by the compound (1) can be obtained by carrying out usual post-treatment operations and purification operations.

For example, in the case of the compound (2-1), the compound (2) can be obtained by a known method, for example, by reducing the following compound (5) to obtain the compound (6), followed by halogenation and synthesis.
R-Cy-Cy-COOH (5)
_{R-Cy-Cy-CH 2} OH (6)
_{R-Cy-Cy-CH 2} Cl (2-1)

  The compound (1) of the present invention can obtain a liquid crystal composition having excellent performance by mixing at least one of them with other liquid crystal compounds and / or non-liquid crystal compounds. For example, when compound (1) is added to a conventional liquid crystal composition, effects such as a reduction in viscosity and optimization of elastic constants can be expected.

  0.1-30 weight part is preferable with respect to 100 weight part of liquid crystal compositions, and, as for the quantity of the compound (1) in a liquid-crystal composition, 1-10 weight part is especially preferable.

  The compound other than the compound (1) in the liquid crystal composition varies depending on the use and required performance of the liquid crystal composition, but usually contains a liquid crystal compound and a compound having a structure similar to the liquid crystal compound as a main component. 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 has 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 liquid crystal electro-optical element is used in various modes such as TN, STN, guest-host (GH), dynamic scattering, phase change, DAP, dual frequency drive, and ferroelectric liquid crystal display. it can.

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, etc. 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.

  Furthermore, 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 polychromatic 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. Ph and Cy have the same meaning as described above.

(Example 1)
Compound (3-a) was synthesized from compound (2-a), and compound (1-a) was synthesized from compound (3-a).
_{C 3 H 7 -Cy-Cy-} CH 2 Cl (2-a)
_{C 3 H 7 -Cy-Cy-} CH 2 CF = CF 2 (3-a)
_{C 3 H 7 -Cy-Cy-} CH 2 CF = CFCH 2 -Cy-C 4 H 9 (1-a)

(Process 1)
Synthesis of Compound (3-a) 3.3 g of metallic lithium, 12.5 g of 4,4′-di-tert-butylbiphenyl and 400 mL of THF were added to a 2 L four-necked flask substituted with argon, and the mixture was stirred at room temperature. Three hours later, the reaction solution was cooled to −10 ° C., 40 mL of a THF solution containing 40 g (0.156 mol) of the compound (2-a) synthesized by a known method was added, and the mixture was stirred for 3 hours. Next, after cooling to -70 ° C., 7.5 L of 60% tetrafluoroethylene / nitrogen gas was passed through the reaction solution and stirred for 1 hour. The reaction solution was gradually warmed to 0 ° C., 400 mL of 2N hydrochloric acid aqueous solution was added, and the mixture was extracted with 500 mL of hexane. The hexane solution was washed with 200 mL of water, 200 mL of sodium bicarbonate water, and 200 mL of water in this order, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 35.4 g of compound (3-a) (0.117 mol, yield 70%).

¹ H-NMR (300 MHz, CDCl ₃ ) 0.84-1.80 (m, 19H), 1.71-1.80 (m, 8H), 2.06-2.19 (m, 2H)
¹⁹ F-NMR (283 MHz, CFCl ₃ ) -106.31 (dd, J = 33.63 Hz, 91.58 Hz, 1F), −125.49 (dd, J = 91.58 Hz, 112.78 Hz, 1F), −172.26 (ddt, J = 24.31 Hz, 30.53 Hz, 112.78 Hz, 1F)

(Process 2)
Synthesis of Compound (1-a) 0.30 g of metallic lithium, 1.1 g of 4,4′-di-tert-butylbiphenyl and 36 mL of THF were added to a 300 mL four-necked flask substituted with argon, and the mixture was stirred at room temperature. After 3 hours, the mixture was cooled to −10 ° C., 5.3 mL of a solution of trans-4-butyl-cyclohexylmethyl chloride synthesized by a known method (2.61 g, 0.014 mol) in THF was added, and the mixture was stirred for 3 hours. Next, 8 mL of a THF solution containing 3.57 g (0.012 mol) of the compound (3-a) was added. After stirring at -70 ° C for 1 hour, the temperature was gradually raised to room temperature. 30 mL of 2N hydrochloric acid aqueous solution was added to the reaction liquid, and extracted twice with 30 mL of hexane. The hexane solution was washed with water (20 mL), sodium bicarbonate water (20 mL), and water (20 mL) in this order, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solvent hexane) to obtain 2.65 g of compound (1-a) (0.006 mol yield 50%).

¹ H-NMR (300 MHz, CDCl ₃ ) 0.84-1.28 (m, 34H), 1.47-1.76 (m, 12H), 2.14-2.27 (m, 4H)
¹⁹ F-NMR (283 MHz, CFCl ₃ ) -152.69 (m, 2F)

  Compound (1-a) had a C-Sm transition temperature of 70.9 ° C, an Sm-Ne transition temperature of 80.3 ° C, and an Ne-I transition temperature of 82.0 ° C. C is a crystal phase, Sm is a smectic phase, Ne is a nematic phase, and I is an isotropic liquid phase.

(Example 2)
Compound (3-b) was synthesized from compound (2-b), and compound (1-b) was synthesized from compound (3-b).
_{C 3 H 7 -Cy-CH 2} Cl (2-b)
_{C 3 H 7 -Cy-CH 2} CF = CF 2 (3-b)
_{C 3 H 7 -Cy-CH 2} CF = CFCH 2 -Ph-F (1-b)

(Process 1)
Synthesis of Compound (3-b) 9.52 g of metal lithium, 36.5 g of 4,4′-di-tert-butylbiphenyl and 800 mL of THF were added to a 2 L four-necked flask substituted with argon, and the mixture was stirred at room temperature. After 3 hours, the mixture was cooled to −10 ° C., 240 mL of a THF solution containing 80 g (0.458 mol) of the compound (2-b) synthesized by a known method was added, and the mixture was stirred for 3 hours. Next, after cooling to -70 ° C., 21 L of 60% tetrafluoroethylene / nitrogen gas was passed through the reaction solution and stirred for 1 hour. The reaction solution was gradually warmed to 0 ° C., added with 2N aqueous hydrochloric acid (800 mL), and extracted with hexane (500 mL). The hexane solution was washed with 270 mL of water, 270 mL of sodium bicarbonate water, and 270 mL of water in this order, and then the solvent was distilled off. Purification by distillation gave 59.7 g (0.271 mol, yield 60%) of compound (3-b).

b. p. 86.0 ° C to 87.4 ° C
¹ H-NMR (300 MHz, CDCl ₃ ) 0.85-1.34 (m, 19H), 1.53-1.77 (m, 8H), 2.07-2.20 (m, 2H)
¹⁹ F-NMR (283 MHz, CFCl ₃ ) -106.39 (dd, J = 30.52 Hz, 88.47 Hz, 1F), −125.49 (dd, J = 85.36 Hz, 109.67 Hz, 1F), 172.27 (ddt, J = 24.31 Hz, 30.53 Hz, 115.89 Hz, 1F)

(Process 2)
Synthesis of Compound (1-b) 665 mg of magnesium metal, 5 mL of THF, and 1 piece of iodine were added to a nitrogen-substituted 300 mL four-necked flask and stirred at room temperature. Then, dropwise addition of 25 mL of a THF solution of 3.95 g (0.027 mol) of p-fluorobenzyl chloride synthesized by a known method was started. During the dropwise addition, the reaction temperature was controlled to be 45 ° C. or lower. After completion of dropping, the mixture was further stirred at 40 ° C. for 1 hour. After cooling the reaction solution to room temperature, 10 mL of a THF solution of 2.0 g (0.009 mol) of (3-b) was added dropwise and stirred at 50 ° C. for 48 hours. The reaction solution was cooled, 30 mL of 2N aqueous hydrochloric acid solution was added, and the mixture was extracted twice with 30 mL of hexane. The hexane solution was washed with water (20 mL), sodium bicarbonate water (20 mL), and water (20 mL) in this order, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solvent hexane) to obtain 1.27 g (0.004 mol, yield 44%) of compound (1-b).

¹ H-NMR (300 MHz, CDCl ₃ ) 0.85-1.76 (m, 17H), 2.20-2.31 (m, 2H), 3.59-3.68 (m, 2H), 6 .96-7.25 (m, 4H)
¹⁹ F-NMR (283 MHz, CFCl ₃ ) -116.93 (d, J = 6.22 Hz, 1F), −151.82 (dt, J = 24.59 Hz, 124.93 Hz, 1F), −154.72. (Dt, J = 24.31 Hz, 125.21 Hz, 1F)

(Example 3)
Compound (3-c) was synthesized from compound (2-c), and compound (1-c) was synthesized from compound (3-c).
_{C 2 H 5 -Cy-Ph-} CH 2 Cl (2-c)
_{C 2 H 5 -Cy-Ph-} CH 2 CF = CF 2 (3-c)
_{C 2 H 5 -Cy-Ph-} CH 2 CF = CFCH 2 -Ph-F (1-c)

(Process 1)
Synthesis of Compound (3-c) 1.02 g of metal magnesium, 10 mL of THF, and 1 piece of iodine were added to a 200 mL four-necked flask purged with nitrogen, and stirred at room temperature. Next, dropwise addition of 90 mL of a THF solution of 10 g (0.042 mol) of the compound (2-c) synthesized by a known method was started. During the dropwise addition, the reaction temperature was controlled to be 45 ° C. or lower. After completion of dropping, the mixture was further stirred at 40 ° C. for 1 hour. The reaction solution was cooled to −30 ° C., and 2 L of 60% tetrafluoroethylene / nitrogen gas was passed through the reaction solution. The reaction was gradually warmed to room temperature and stirred for 24 hours. 50 mL of 2N hydrochloric acid aqueous solution was added to the reaction solution, and the mixture was extracted with 100 mL of hexane. The hexane solution was washed with 50 mL of water, 50 mL of sodium bicarbonate water, and 50 mL of water in this order, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solvent hexane) to obtain 5.01 g of compound (3-c) (0.018 mol yield 43%).

¹⁹ F-NMR (283 MHz, CFCl ₃ ) -106.12 (dd, J = 33.63 Hz, 88.47 Hz, 1F), −125.06 (dd, J = 85.36 Hz, 115.89 Hz, 1F), -172.69 (ddt, J = 24.31 Hz, 30.53 Hz, 112.78 Hz, 1F)

(Process 2)
Synthesis of Compound (1-c) 3.44 g of metal magnesium, 50 mL of THF, and 1 piece of iodine were added to a nitrogen-substituted 200 mL four-necked flask and stirred at room temperature. Subsequently, dropwise addition of 50 mL of a THF solution of 12.8 g (0.088 mol) of p-fluorobenzyl chloride synthesized by a known method was started. During the dropwise addition, the reaction temperature was controlled to be 45 ° C. or lower. After completion of dropping, the mixture was further stirred at 40 ° C. for 1 hour. After cooling the reaction solution to room temperature, 10 mL of a THF solution of 4.3 g (0.015 mol) of compound (3-c) was added dropwise, and the mixture was stirred at 50 ° C. for 24 hours. The reaction solution was cooled, 50 mL of 2N hydrochloric acid solution was added, and the mixture was extracted twice with 50 mL of hexane. The hexane solution was washed with 50 mL of water, 50 mL of sodium bicarbonate water, and 50 mL of water in this order, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solvent hexane) to obtain 1.81 g (0.005 mol, yield 33%) of compound (1-c).

¹ H-NMR (300 MHz, CDCl ₃ ) 0.88-1.90 (m, 9H), 2.41-3.70 (m, 4H) 6.96-7.25 (m, 8H)
¹⁹ F-NMR (283 MHz, CFCl ₃ ) -116.73 (d, 7.07 Hz, 1F), −152.92 (dt, J = 24.59 Hz, 128.04 Hz, 1F), −154.37 (dt , J = 24.30Hz, 124.93Hz, 1F)

  The fluorine-containing compound of the present invention can be synthesized industrially easily and simply, and can be used for applications requiring functionality such as liquid crystal compositions.

Claims (8)

A fluorine-containing compound represented by the following formula (1).
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n -A 3 - (CH 2) p -CF = CF- (CH 2) q -A 4 - (Z 3 -A 5) _r- (Z ⁴ -A ⁶ ) _s -R ² (1)
(However, the symbols in the formula have the following meanings.
R ¹ and R ² : independently of each other, a hydrogen atom, a halogen atom, or a monovalent 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 In addition, an etheric oxygen atom or a thioetheric sulfur atom may be inserted.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ : independently of one another, a phenylene group or a cyclohexylene group. However, one or more hydrogen atoms in the groups A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ may be substituted with a halogen atom, and one or two existing in the group One —CH═ may be substituted with a nitrogen atom, and one or two —CH ₂ — present in the group may be substituted with an etheric oxygen atom or a thioetheric sulfur atom. However, two —CH ₂ — are not continuously substituted by an etheric oxygen atom or a thioetheric sulfur atom.
Z ¹ , Z ² , Z ³ , Z ⁴ : each independently a single bond, —O—, —S—, or a divalent aliphatic hydrocarbon group having 1 to 4 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 In addition, an etheric oxygen atom or a thioetheric sulfur atom may be inserted.
m, n, r, s: 0 or 1 independently of each other.
p, q: An integer of 0 to 3 independently of each other. However, p + q is 1 or more. )   The fluorine-containing compound according to claim 1, wherein m + n + r + s is 2 or less in the compound represented by formula (1).   The fluorine-containing compound according to claim 1 or 2, wherein in the compound represented by the formula (1), p and q are both 1. The fluorine-containing compound according to any one of claims 1 to 3, wherein in the compound represented by the formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are all single bonds. In the compound represented by the formula (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a 1,4-cyclohexylene group or a 1,4-phenylene group. The fluorine-containing compound according to any one of claims 1 to 4, wherein one or more hydrogen atoms present in the 1,4-phenylene group may be substituted with a fluorine atom. The compound represented by formula (2) is metallized, this is reacted with tetrafluoroethylene to synthesize the compound represented by formula (3), and the compound represented by formula (4) is similarly metallized. The manufacturing method of the compound represented by Formula (1) by making the obtained compound react with the compound represented by Formula (3).
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -X (2)
R ^1- (A ¹ -Z ¹ ) _m- (A ² -Z ² ) _n -A ^3- (CH ₂ ) _p -CF = CF ₂ (3)
^{_{X- (CH 2) q -A 4}} - (Z 3 -A 5) r - (Z 4 -A 6) s -R 2 (4)
^{R 1 - (A 1 -Z 1} ) m - (A 2 -Z 2) n -A 3 - (CH 2) p -CF = CF- (CH 2) q -A 4 - (Z 3 -A 5) _r- (Z ⁴ -A ⁶ ) _s -R ² (1)
(Wherein, X is chlorine atom, a bromine atom or an iodine ^{atom, R 1, R 2, A} 1, A 2, A 3, A 4, A 5, A 6, Z 1, Z 2, Z 3, Z ⁴ , m, n, p, q, r, and s have the same meaning as described above.)   A liquid crystal composition containing the fluorine-containing compound according to claim 1.   A liquid crystal electro-optical element in which the liquid crystal composition according to claim 7 is sandwiched between substrates with electrodes.