JP2001348371A - Difluorobenzonitrile compound, its intermediate, method for producing the same, liquid crystalline composition and liquid crystalline electric optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound used as a liquid crystalline electronic optical element capable of being driven at a low electric voltage and excellent in displaying quality. SOLUTION: This difluorobezonitrile compound is expressed by formula (1) [wherein, R is an aliphatic hydrocarbon group or the like; X is oxygen atom or a single bond; A1, A2, A3 are each 1,4-phenylene group, trans-1,4- cyclohexylene group or the like; Y is CH2CH2, OCH2, CH2O, O, CF=CF, C≡C, a single bond or the like; (m), (n) are each 0-4; and (q), (r) are each 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a difluorobenzonitrile compound used for a liquid crystal electro-optical element, an intermediate thereof, a liquid crystal composition containing the compound, and a liquid crystal electro-optical element using the liquid crystal composition.

[0002]

2. Description of the Related Art A liquid crystal electro-optical element using a liquid crystal material is:
Including display devices for OA equipment, portable devices, display devices for home appliances, watches, calculators, measuring instruments, automotive instruments, copiers,
It is used for various applications such as cameras, and demands various performances such as a wide operating temperature range, low operating voltage, high-speed response, and chemical stability. However, at present, there is no compound that satisfies all of these characteristics alone, and a plurality of liquid crystal compounds and / or non-liquid crystal compounds excellent in one or more characteristics are mixed to obtain the required performance as a liquid crystal composition. Meets.

[0003] In the field of display devices using liquid crystals, among various characteristics required for liquid crystal compounds, they are excellent in compatibility with other liquid crystal materials or non-liquid crystal materials, are chemically stable, and have a liquid crystal electric property. It is an important subject to provide a compound having a property that can be driven at a low voltage when used for an optical element. As a solution to such a problem, the following difluorobenzonitrile compounds are disclosed. (I), (ii): JP-A-62-103057 (iii): JP-A-1-131144 (iv): JP-A-3-130253

[0004]

Embedded image These compounds are compounds that can be driven at a low voltage when used in a liquid crystal electro-optical element, and are chemically stable. However, the demands on viewing angle characteristics, low-voltage driving properties, contrast, and visibility are becoming more severe, and the development of compounds that can further improve the display quality of liquid crystal electro-optical elements while maintaining low-voltage driving properties has been developed. Is expected.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid crystal composition suitable for obtaining a liquid crystal electro-optical element which can be driven at a low voltage and has a high display quality, and a compound to be contained therein. I do.

[0006]

The present inventors have focused on compounds having an alkenyl group and a difluorobenzonitrile group to solve the above-mentioned problems, and as a result of various studies, have found that among compounds having these groups, When a compound having a specific structure is contained in a liquid crystal composition, a liquid crystal electro-optical element using the liquid crystal composition can be driven at a low voltage and can improve the display quality of the liquid crystal electro-optical element. Heading, the present invention has been completed.

Japanese Patent Application Laid-Open No. 4-296387 describes a formula including a difluorobenzonitrile compound having an alkenyl group, but describes specific compound names of the difluorobenzonitrile compound having an alkenyl group. Further, there is no description of physical data, physical properties of liquid crystal, and the like, and no description is given of the effect of having an alkenyl group. Further, a conventionally known production method (for example, the above publication, Japanese Patent Application Laid-Open No. 62-103057).
In the production method described in Japanese Unexamined Patent Application Publication No. H11-131144 or Japanese Unexamined Patent Publication No. HEI 3-130253),
In the case of a compound having a double bond such as an alkenyl group in the terminal group, it cannot be easily produced due to the reactivity of the double bond in the terminal group.

The present invention provides a difluorobenzonitrile compound represented by the formula (1) (hereinafter, also referred to as “compound (1)”).

Embedded imageHowever, symbols in the formulas have the following meanings throughout this specification.
You. R: an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom. -CH = CH-: a trans-vinylene group. X: oxygen atom or single bond. A¹, A^Two: Independently of each other, 1,4-phenylene group
Or a trans-1,4-cyclohexylene group. A¹And
And A^TwoGroups are each unsubstituted or substituted
And one or more halogen atoms or methyl groups
May have, A¹And A^Two1 existing in the group of
One or more CH groups are replaced by nitrogen atoms
Or one or more CH_TwoThe group is an oxygen atom or
May be substituted by a sulfur atom. A^Three: A trans-1,4-cyclohexylene group or
1,4-phenylene group. A^ThreeIs trans-1,4-sig
In the case of a rohexylene group, this group may be unsubstituted or
Represents one or more halogen atoms as substituents or
May have a methyl group, and up to one
Or two or more CH groups may be substituted with a nitrogen atom
One or more CH_TwoThe group is an oxygen atom or sulfur
It may be substituted by a yellow atom. A^ThreeIs 1,4-phenyl
In the case of a benzene group, this group may be substituted by one or more
Having the above halogen atom or methyl group,
One or more existing CH groups are replaced with nitrogen atoms
It may be. Y: -CH_TwoCH_Two-, -CH_Two-, -CH = CH-,
-OCH_Two-, -CH _TwoO-, -O-, -CF = CF
-, -C≡C- or a single bond. m, n: 0, 1, 2, 3, or 4 independently of each other. q, r: 0 or 1 independently of each other. However, A^TwoIs an unsubstituted 1,4-phenylene group,
When q is 1, Y is a single bond, and r is 0,
A¹Is not an unsubstituted 1,4-phenylene group. formula
In (1), r is preferably 0. Also, if r is 0
And A^TwoIs unsubstituted trans-1,4-cyclohexyl
It is preferably a silene group.

The present invention also provides a difluorobenzene compound represented by the formula (2) which is also an intermediate of the compound (1) (hereinafter also referred to as “compound (2)”).

[0010]

Embedded image

Further, the present invention provides a Grignard reagent by reacting a compound represented by the formula (3) with magnesium metal, and then reacts with the compound represented by the formula (4) in the presence of a transition metal catalyst. Equation (2) characterized by
A method for producing a difluorobenzene compound represented by the formula:

[0012]

Embedded image However, the symbols in the formula have the following meanings throughout this specification. B ¹ : chlorine atom, bromine atom or iodine atom. B ² : a leaving group. Further, the present invention provides a method for producing a difluorobenzonitrile compound of the formula (1), which goes through the above-mentioned production step. The present invention also provides a liquid crystal composition containing at least one difluorobenzonitrile compound of the formula (1),
Further, the present invention provides a liquid crystal electro-optical element in which the liquid crystal composition is sandwiched between substrates having electrodes.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the formula (1) of the present invention is a difluorobenzonitrile compound having an alkenyl group (hereinafter, the compound represented by the formula (1) may be referred to as the compound (1)). Write).

In the compound (1), R represents 1 to 5 carbon atoms.
Is an aliphatic hydrocarbon group or a hydrogen atom. Carbon number 1
The aliphatic hydrocarbon group having 5 carbon atoms has 1, 2, 3, 4 carbon atoms.
Or 5 linear or branched alkyl groups.
You. In particular, high compatibility, T _cTend to be high
And a linear alkyl group or a hydrogen atom is preferred. X is an acid
It is an element atom or a single bond. M and n are mutually independent
0, 1, 2, 3 or 4. X is an oxygen atom
In this case, m + n is preferably 1 or 3. X is a single bond
In this case, m + n is preferably 0, 2 or 4. X is a single bond
This is preferable because the viscosity is low.

In the compound (1), R-CH = CH-
(CH) _m -X- (CH) _n- (hereinafter, also referred to as a terminal group Z) is specifically preferably a group as shown below.
Examples of the terminal group Z in which X is a single bond include vinyl group, allyl group, trans-1-propenyl group, 3-butenyl group, trans-1-butenyl group, 4-pentenyl group, trans-3-pentenyl group, trans -1-pentenyl group, 5
-Hexenyl group, trans-3-hexenyl group, trans-1-hexenyl group, 6-heptenyl group, trans-
Preferred examples include a 5-heptenyl group, a trans-3-heptenyl group, a trans-1-heptenyl group, a 7-octenyl group, a trans-5-octenyl group, a trans-3-octenyl group, and a trans-1-octenyl group. Examples of the terminal group Z in which X is an oxygen atom include a vinyloxy group, an allyloxy group, a 2-propenyloxy group, a 3-butenyloxy group, a trans-2-butenyloxy group, a 4-pentenyloxy group, a trans-3-pentenyloxy group,
Trans-2-pentenyloxy group, 5-hexenyloxy group, trans-4-hexenyloxy group, trans-2-hexenyloxy group, vinyloxymethyl group, allyloxymethyl group, 1-propenyloxymethyl group,
3-butenyloxymethyl group, trans-1-butenyloxymethyl group, 4-pentenyloxymethyl group, trans-3-pentenyloxymethyl group, trans-1-
Pentenyloxymethyl group, 5-hexenyloxymethyl group, trans-3-hexenyloxymethyl group, trans-1-hexenyloxymethyl group, trans-2-
Heptenyloxy, trans-4-heptenyloxy,
2- (vinyloxy) ethyl group, 2- (allyloxy)
Ethyl group, 2- (1-propenyloxy) ethyl group, 2
-(3-butenyloxy) ethyl group, 2- (trans-
2-butenyloxy) ethyl group, 2- (4-pentenyloxy) ethyl group, 2- (trans-2-pentenyloxy) ethyl group, 3- (vinyloxy) propyl group,
-(Allyloxy) propyl group, 3- (1-propenyloxy) propyl group, 3- (3-butenyloxy) propyl group, 3- (trans-1-butenyloxy) propyl group, 4- (vinyloxy) butyl group, Preferred are (allyloxy) butyl group and 4- (1-propenyloxy) butyl group.

A ¹ and A ² are each independently 1,4-
It is a phenylene group or a trans-1,4-cyclohexylene group. The groups A ¹ and A ² each may be unsubstituted or have one or more halogen atoms or methyl groups as substituents, and A ¹ and A 2
One or more CH groups present in group ² may be substituted with a nitrogen atom, and one or more C
The H ₂ group may be substituted by an oxygen atom or a sulfur atom. When a halogen atom is contained as a substituent, the value of Δε is further increased. As the halogen atom, a fluorine atom is preferable because of its low viscosity. The positions of these substituents are not limited.

A ¹ and A ² are, for example, unsubstituted 1,4-phenylene group, unsubstituted trans-1,4-cyclohexylene group, 3-fluoro-1,4-phenylene group or 3,5 A difluoro-1,4-phenylene group,
2,5-pyrimidinylene group, 2,5-pyridinylene group,
Examples thereof include a 3-methyl-1,4-phenylene group and a 1,3-dioxane-2,5-diyl group. In this specification, the 1-position and 4-position of the groups A ¹ , A ² and A ³
Regarding the position of the place, the one closer to R in equation (1) is always the first place.

A ³ is a trans-1,4-cyclohexylene group or a 1,4-phenylene group. If A ³ is trans-1,4-cyclohexylene group, the group may have one or more halogen atoms or a methyl group as or substituent which is unsubstituted, A ³ One or more CH groups present in the group may be substituted with a nitrogen atom, and one or more CH ₂ groups may be substituted with an oxygen atom or a sulfur atom. When A ³ is a 1,4-phenylene group, this group has one or more halogen atoms or methyl groups as substituents,
One or more CH groups may be substituted by a nitrogen atom. When the compound has a halogen atom, the same effect as described above is expected. The positions of these substituents are not limited. A ³ includes, for example, unsubstituted trans-1,
4-cyclohexylene group, 1,3-dioxane-2,5
-Diyl group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 3-methyl-1,4-phenylene group and the like. Among these, an unsubstituted trans-1,4-cyclohexylene group is preferable from the viewpoint of lowering the viscosity and improving the liquid crystallinity. 3-fluoro-1,4
-A phenylene group or a 3,5-difluoro-1,4-phenylene group is preferred.

Y is -CH ₂ CH _2- , -CH ₂ -,-
_{CH = CH -, - OCH 2} -, - CH 2 O -, - O-,
-CF = CF-, -C≡C- or a single bond. Of _{these, -CH 2 CH 2 -, -} OCH 2 -, - C
H ₂ O—, —C≡C—, and a single bond are preferred in terms of liquid crystallinity. q and r are independently 0 or 1; When importance is attached to low viscosity, r is preferably 0. q
Is preferably 0 from the viewpoint of low viscosity. In particular, a compound in which r is 0 and A ² is an unsubstituted trans-1,4-cyclohexylene group has a further lower viscosity and is preferred.

Preferred examples of the compound (1) are shown below classified into the number of r. In the following description, "-Ph
"-" Represents an unsubstituted 1,4-phenylene group, and "-Cy-" represents an unsubstituted trans-1,4-cyclohexylene group. "-Ph ^FF CN" is 3,5-difluoro-4
- cyanophenyl groups (the following formulas (v)), "- Ph ^FF -" is 3,5-difluoro-1,4-phenylene group (the following formulas (v
i)), "- Ph ^F -" indicates 3-fluoro-1,4-phenylene group (the following formula (vii)).

[0021]

Embedded image

In the formula (1), r is 0 and A ²
Is a non-substituted trans-1,4-cyclohexylene group, specifically, the compounds shown below. Of these, bicyclic compounds have particularly low viscosity and are suitable for increasing the response speed of the liquid crystal electro-optical element. Further, the tricyclic compound exhibits liquid crystallinity up to a relatively high temperature range, and is a compound suitable for driving a liquid crystal electro-optical element in a wide temperature range. R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ ^{- Ph FF CN R-CH =} CH- (CH 2) m -O- (CH 2) n -Cy-Cy-CH 2 CH 2 -Ph FF CN R-CH = CH- (CH 2) m + n - Cy-Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ O-Cy-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O-Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ O-Cy-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O-Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-OCH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-OCH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Ph-OCH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-OCH ₂ -Cy-CH ₂ CH ₂ -Ph ^FF CN

Further, among the compounds in which r in formula (1) is 0, examples of the compound wherein A ² is an unsubstituted 1,4-phenylene group include the following compounds. . Of these, compounds having three rings exhibit liquid crystallinity up to a relatively high temperature range, and are suitable for driving a liquid crystal electro-optical element in a wide temperature range. R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ ^{- Ph FF CN R-CH =} CH- (CH 2) m -O- (CH 2) n -Cy-Ph-CH 2 CH 2 -Ph FF CN R-CH = CH- (CH 2) m + n - Cy-Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ O-Ph-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O-Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ O-Ph-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O-Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-OCH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-OCH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Ph-OCH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-OCH ₂ -Ph-CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Ph -C≡C-Ph-CH ₂ CH ₂ -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph -C≡C-Ph-CH ₂ CH ₂ -Ph ^FF CN

In the compound in which r in formula (1) is 0, one of A ¹ and A ² or A ¹ and A 2
Compounds as shown in the following specific examples, in which both of ² are 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group, have a larger value of Δε, and It is suitable for lowering the driving voltage of the electro-optical element. R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH -(CH ₂ ) _{m + n} -Cy-Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^F -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- ( CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- ( CH ₂ ) _n -Cy-CH ₂ O- Ph ^F -CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O- Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- ( CH ₂ ) _n -Ph-CH ₂ CH ₂ -Ph ^F -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- ( CH ₂ ) _n -Ph-CH ₂ O- Ph ^F -CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O- Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ O- Ph ^FF -CH ₂ CH ₂ -Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O- Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph ^F -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH
₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^F -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m- O- (CH ₂ ) _n -Ph ^F -CH ₂ CH ₂ -Ph ^F -CH ₂ CH
₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^F -CH ₂ CH ₂ -Ph ^F -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m- O- (CH ₂ ) _n -Ph ^FF -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH
₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m- O- (CH ₂ ) _n -Ph ^F -CH ₂ O-Ph ^FF -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^F -CH ₂ O-Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- ( CH ₂ ) _n -Ph ^FF -CH ₂ O-Ph ^FF -CH ₂ CH _2-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -CH ₂ O-Ph ^FF -CH ₂ CH ₂ -Ph ^FF CN

Further, among the compounds (1), the compound wherein r is 1 includes the following compounds. Among them, the three-ring compound exhibits liquid crystallinity up to a relatively high temperature range, and is a compound suitable for driving a liquid crystal electro-optical element in a wide temperature range. Further, the four-ring compound exhibits liquid crystal properties even in a high temperature range, and is a compound suitable for driving a liquid crystal electro-optical element in a high temperature range. R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-Ph-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy- Cy-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Cy-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-Ph-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-Ph-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-Cy-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n-} Ph-Cy-CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ O-Ph-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O-Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ O-Cy-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O-Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ O-Ph-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O-Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-CH ₂ O-Cy-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ O-Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-OCH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-OCH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-OCH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-OCH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-OCH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-OCH ₂ -Ph-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph-OCH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph
^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-OCH ₂ -Cy-CH ₂ CH ₂ -Cy-Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph -C≡C-Ph-CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph -C≡C-Ph-CH ₂ CH ₂ -Cy- Ph ^FF CN

Further, in the compound (1), r is 1,
One or more of A ¹ , A ² and A ³ is 3
A compound such as a -fluoro-1,4-phenylene group or a 3,5-difluoro-1,4-phenylene group as shown in the following specific examples exhibits liquid crystallinity up to a relatively high temperature range and has a Δε The value is further increased, which is suitable for lowering the driving voltage of the liquid crystal electro-optical element. R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-Ph ^F -CH ₂ CH ₂ -Cy- Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph ^F -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Cy-Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Ph-Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n- Ph ^FF -Ph ^FF -CH ₂ CH ₂ -Cy-
Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^F -CH ₂ CH _2-
Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^F -CH ₂ CH ₂ -Cy- Ph ^FF
CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH _2-
Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF
CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph ^FF -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH
₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -CH ₂ CH ₂ -Ph ^FF -CH ₂ CH ₂ -Cy- Ph
^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph ^FF -CH ₂ O-Ph ^FF -CH ₂ CH _2-
Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^FF -CH ₂ O- Ph ^FF -CH ₂ CH ₂ -Cy- Ph
^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ O- Ph ^FF -CH ₂ CH ₂ -Cy
-Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ O- Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O -(CH ₂ ) _n -Cy-OCH ₂ -Ph ^FF -CH ₂ CH ₂ -Cy
-Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-OCH ₂ -Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Ph -C≡C-Ph ^FF -CH ₂ CH ₂ -Cy
-Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph -C≡C-Ph ^FF -CH ₂ CH ₂ -Cy- Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^F -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph ^F -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph-CH ₂ CH ₂ -Ph ^F -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _m -O- (CH ₂ ) _n -Cy-Ph-CH ₂ CH ₂ -Ph ^FF -Ph ^FF
CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-Cy-CH ₂ CH ₂ -Ph ^F -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph-Cy-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Cy-CH ₂ CH ₂ -Ph ^F -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Cy-CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Ph ^F -CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN R-CH = CH _{- (CH 2) m + n} - Ph FF -CH 2 CH 2 -Ph FF - Ph FF CN R-CH = CH- (CH 2) m + n -Cy-Ph F -CH 2 CH 2 -Ph FF - Ph ^FF CN R-CH = CH- (CH ₂ ) _{m + n} -Cy-Ph ^FF -CH ₂ CH ₂ -Ph ^FF -Ph ^FF CN In the above description, A ¹ and A ² are 1,4- Although a specific example of a case of a phenylene group or a trans-1,4-cyclohexylene group,, a ¹ and a ² are 2,5
-Pyrimidinylene group, 2,5-pyridinylene group, 1,3
-Dioxane-2,5-diyl group, 3-methyl-1,4
A compound substituted with a phenylene group or the like is also appropriately selected.
Similarly, a compound in which A ³ is substituted with a 1,3-dioxane-2,5-diyl group or the like is appropriately selected.

Compound (1) can be easily produced industrially according to the following method.

Embedded image That is, the compound represented by the formula (3) is reacted with metallic magnesium to obtain a Grignard reagent. In the formula (3), B ¹ represents a chlorine atom, a bromine atom or an iodine atom, but from the viewpoint of reactivity and stability, B ¹ is preferably a bromine atom. As the solvent, an ether solvent is preferable, and industrially, tetrahydrofuran (THF) or t-butyl methyl ether (MTBE) is particularly preferable. The resulting Grignard reagent is reacted with a compound of the formula (4) in the presence of a transition metal catalyst to give a compound of the formula (2)
And the compound of In the formula (4), B ² may be any group having the property of being eliminated during the reaction, and is appropriately selected depending on the reaction conditions and the type of the catalyst. Among them, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, an acetoxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group are preferred, and a bromine atom or p
-A toluenesulfonyloxy group is particularly preferred. As the transition metal catalyst, a copper-based compound, in particular, copper (I) iodide, copper (I) cyanide, copper (II) acetate and the like are preferable from the viewpoint of reactivity and cost. The reaction is carried out in a solvent. As the solvent, an ether-based solvent is preferable.
Alternatively, MTBE is preferred. It is also effective and preferable to use a hydrocarbon solvent such as toluene or hexane in combination in order to suppress a side reaction. The reaction temperature varies depending on the leaving group, the catalyst used, and the solvent.
The temperature is preferably about 100 ° C, particularly preferably about -50 ° C to + 30 ° C.

From the obtained compound (2), compound (1)
There are various methods for obtaining, but it can be industrially produced, for example, by the following method. That is, the compound (2) is lithiated with a lithiating agent and then reacted with carbon dioxide to obtain a carboxylic acid compound of the formula (7). As a lithiating agent, butyllithium is preferred in terms of reactivity and cost. The reaction is carried out in a solvent, and the solvent is preferably an ether solvent, and industrially, THF or MTBE is particularly preferable. The reaction temperature is
-100 ° C, depending on the lithiating agent and solvent used
To about 0 ° C, and more preferably about -70 ° C to about -20 ° C.

The obtained carboxylic acid (7) is halogenated with a halogenating agent to obtain an acid halide (8). As the halogenating agent, thionyl chloride, oxalyl chloride and the like are industrially preferable. Although a catalyst may or may not be added, it is effective and preferable to add N, N-dimethylaniline, triethylamine, pyridine or the like as a catalyst. The reaction may be carried out without solvent or with a solvent, but from the viewpoint of workability and the like, it is preferable to use tetrachloroethylene, dichloromethane, dichloroethane or the like as the solvent. The reaction temperature depends on the presence or absence of the catalyst and the solvent.
To about 100 ° C. The obtained acid halide (8) is reacted with ammonia or amine to form an acid amide (9). Ammonia is preferably used as the reactant industrially. The reaction may be carried out without a solvent or with a solvent, but it is preferable to use toluene or the like as a solvent from the viewpoint of workability.
Further, the carboxylic acid (7) can be directly amidated with an amidating agent to give an acid amide (9).

The desired compound (1) can be obtained by reacting the thus obtained acid amide (9) with a dehydrating agent. As the dehydrating agent, thionyl chloride or p-toluenesulfonic acid chloride-pyridine is preferred. Although various solvents can be used as the reaction solvent, toluene and the like are industrially preferable. The reaction temperature is
0 ° C to 200 ° C, depending on the dehydrating agent and solvent used
Degree is preferable, and about 50 to 150 ° C. is particularly preferable. Alternatively, the desired compound (1) can also be obtained by lithiating the compound (2) with a lithiation agent and then directly reacting the compound (2) with a cyanogen compound. Examples of the cyanogen compound include dicyan and chlorocyan.

The method for producing the compound (3) used in the reaction is not particularly limited, and it can be produced by a commonly used method.
For example, it can be produced according to the following synthetic route. 1. A ¹ = 1,4-phenylene group, q = 1, n = 1 to 3
in the case of

Embedded image Compound (a) is dissolved in a solvent such as hexane, and 3,4-dihydro-2H- is dissolved in the presence of Amberlyst 15 (ion-exchange resin manufactured by Rohm and Haas Co.) as a catalyst.
Stir with pyran to obtain compound (b). Next, the compound (c) is dissolved in THF, and a solution in which metallic magnesium is dissolved in THF is added dropwise thereto. After stirring for about 2 hours, the reaction solution was cooled, and the reaction solution was mixed with compound (b) and Ni (dp
pe) is added dropwise to a solution of ₂ Cl ₂ solvent. The mixture is heated to room temperature, a saturated aqueous solution of ammonium chloride is added, and the mixture is stirred for about 10 minutes. Then, the crystals are filtered and extracted with MTBE to obtain a compound (d). The compound (d) is refluxed in a solvent such as methanol in the presence of Amberlyst 15 to obtain a compound (e). Then, triphenylphosphine (PPh ₃ ) is dissolved in acetonitrile, bromine is added dropwise, and the compound (e) is added dropwise to the reaction solution stirred for about 30 minutes, followed by stirring for about 1 hour. The obtained reaction product is purified to obtain a compound (3-).

2. A ² = 1,4-phenylene group, q =
0, n = 1 to 3

Embedded image Compound (3-) can be obtained in the same manner as in 1.

3. A ¹ = 1,4-phenylene group, q =
1, when X = oxygen atom and n = 0

Embedded image Compound (f) is prepared by compound (g) in the presence of potassium carbonate.
To give compound (h). The resulting compound (h) was brominated in the same manner as 1 to give the compound (3)
-) Is obtained.

4. A ¹ , A ² = trans-1,4-cyclohexylene group, n = 2, 3, 4

Embedded image Compound (i) is acidified with sulfuric acid, one of the hydroxyl groups is brominated,
Compound (j) is obtained. Next, the other hydroxyl group is protected with a tetrahydropyranyl group in the same manner as in 1, to obtain a compound (k). Compound (k) is reacted with metallic magnesium to prepare a Grignard reagent, and then reacted with compound (l) in the presence of copper (II) acetate to obtain compound (m). Next, the tetrahydropyranyl group is deprotected (n) and brominated to obtain a compound (3-).

5. A ² = 1,4-phenylene group, n =
2, 3, 4

Embedded image One hydroxyl group of the compound (o) is protected (p), and the other hydroxyl group is esterified to obtain a compound (q). This is reacted with a Grignard reagent (r) to obtain a compound (s),
Hereinafter, the compound (3-) is obtained in the same manner as in 1.

6. X = single bond, m = 0, n = 0

Embedded image One hydroxyl group of compound (u) is protected (v), and the other hydroxyl group is oxidized to obtain compound (w). Next, a compound (y) is obtained by a Wittig reaction, and a compound (3-) is obtained in the same manner as in 1 below.

7. A ² = 1,4-phenylene group, q =
0, X = oxygen atom, n = 0

Embedded image Compound (3-) can be obtained in the same manner as in 3.

8. X = oxygen atom, n = 1

Embedded image One hydroxyl group of compound (a ′) is protected (b ′), and reacted with compound (c ′) in the presence of sodium hydride to obtain compound (d ′). Hereinafter, the compound (3)
-) Is obtained.

9. A ¹ = trans-1,4-cyclohexylene group, X = oxygen atom, n = 0, q = 1

Embedded image Compound (3-) can be obtained in the same manner as in 8.
Note that these manufacturing methods are merely examples, and various other manufacturing methods can be used.

The compound (1) thus obtained is
It has a very large positive dielectric anisotropy (Δε), is highly compatible with other liquid crystal compounds or non-liquid crystal compounds, and is chemically stable. This is suitable for lowering the drive voltage of the optical element. The compound (1) has a large ratio (K ₃₃ / K ₁₁ ) between the bend elastic constant (K ₃₃ ) and the splay elastic constant (K ₁₁ ), and particularly has a high twist angle super twist nematic (STN) type liquid crystal electric device. When used for optical elements, etc., the voltage-
The transmittance characteristic becomes steep, and a liquid crystal electro-optical element having excellent display quality can be obtained.

Compound (1) is another liquid crystal compound or a non-liquid crystal compound (these compounds are collectively referred to as "other compounds").
And used as a liquid crystal composition. The amount of the compound (1) in the liquid crystal composition can be appropriately changed depending on the use, the purpose of use, the type of other compound, and the like. Is preferable, and 2 to 20% by mass is particularly preferable. Further, the liquid crystal composition may contain two or more types of the compound (1) depending on the use and purpose of use. In this case, the total amount of the compound (1) is preferably 0.5 to 60% by mass, and particularly preferably 2 to 30% by mass, based on the total amount of the liquid crystal composition.

Other compounds used as a mixture with the compound (1) include components for improving dielectric anisotropy, components exhibiting liquid crystallinity at high temperatures, other low-viscosity components, and refractive index anisotropy values. Components, components that impart cholestericity, components that exhibit dichroism, components that impart electrical conductivity, and various other additives are exemplified. These are appropriately selected depending on the application, required performance, and the like, but are usually preferably composed of a liquid crystal compound, a main component having a similar structure to the liquid crystal compound, and additional components added as necessary.

In the liquid crystal composition containing the compound (1),
Other compounds to be included in the liquid crystal composition include, for example, the following. Note that R ¹ and R in the following formula
² represents a group such as an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a halogen atom, and a cyano group. Further, R ¹ and R ² may be the same or different. R ¹ -Cy-Cy-R ² R ¹ -Cy-Ph-R ² R ¹ -Cy-Ph ^FF CN R ¹ -Ph-Ph-R ² R ¹ -Ph-C≡C-Ph-R ² R ¹ -Cy-COO-Ph-R ² R ¹ -Cy-COO-Ph ^FF CNR ¹ -Ph-COO-Ph-R ² R ¹ -Ph-COO-Ph ^FF CNR ¹ -Cy-CH = CH-Ph ^{-R 2 R 1 -Ph-CH =} CH-Ph-R 2 R 1 -Ph-CF = CF-Ph-R 2 R 1 -Cy-CF = CF-Ph-R 2 R 1 -Cy-CF = CF ^{-Cy-R 2 R 1 -Cy-} Ph-CF = CF-Ph-R 2 R 1 -Cy-Ph-CF = CF-Cy-R 2 R 1 -Ph-Cy-CF = CF-Cy-R 2 R ¹ -Cy-Cy-CF = CF-Ph-R ² R ¹ -Ph-Ph-CF = CF-Ph-R ² R ¹ -Cy-CH ₂ CH ₂ -Ph-R ² R ¹ -Cy-Ph − ^{_{H 2 CH 2 -Ph-R 2}} R 1 -Cy-Ph-CH 2 CH 2 -Cy-R 2 R 1 -Cy-Cy-CH 2 CH 2 -Ph-R 2 R 1 -Ph-CH 2 CH 2 ^{-Ph-R 2 R 1 -Ph-} Ph-CH 2 CH 2 -Ph-R 2 R 1 -Ph-Ph-CH 2 CH 2 -Cy-R 2 R 1 -Cy-Ph-Ph-R 2 R 1 ^{-Cy-Ph-Ph FF CN R} 1 -Cy-Ph-C≡C-Ph-R 2 R 1 -Cy-Ph-C≡C-Ph FF CN R 1 -Cy-Ph-C≡C-Ph- ^{Cy-R 2 R 1 -Cy-} CH 2 CH 2 -Ph-C≡C-Ph-R 2 R 1 -Cy-CH 2 CH 2 -Ph-C≡C-Ph-Cy
^{-R 2 R 1 -Cy-Ph-} Ph-Cy-R 2 R 1 -Ph-Ph-Ph-R 2 R 1 -Ph-Ph-C≡C-Ph-R 2 R 1 -Ph-CH 2 CH ₂ -Ph-C≡C-Ph-R ² R ¹ -Ph-CH ₂ CH ₂ -Ph-C≡C-Ph-Cy
^{-R 2 R 1 -Cy-COO-} Ph-Ph-R 2 R 1 -Cy-COO-Ph-Ph FF CN R 1 - Cy- Ph- COO- Ph- R 2 R 1 -Cy-Ph-COO- Ph ^FF CNR ¹ -Cy-COO-Ph-COO-Ph-R ² R ¹ -Cy-COO-Ph-COO-Ph ^FF CNR ¹ -Ph-COO-Ph-COO-Ph-R ² R ^1- Ph-COO-Ph-OCO-Ph-R ² These compounds are merely examples, and a hydrogen atom present in a ring structure or a terminal group in the compound is substituted with a halogen atom, a cyano group, a methyl group, or the like. It may be.
Further, a cyclohexane ring or a benzene ring may be substituted with another six-membered ring or five-membered ring, for example, a pyrimidine ring, a dioxane ring, or the like. group, for _{example, -CH 2 O -, - CH} = CH -, - N =
N -, - CH = N - , - COOCH 2 -, - OCOCH
_It may be changed to _2- , -COCH ₂ -or the like, and these may be selected from various compounds according to the desired performance. The compound (2), which is an intermediate of the compound (1) of the present invention, also has a positive dielectric anisotropy, and is excellent in compatibility with other compounds. The compound (2) is mixed with another compound in the same manner as the compound (1), and can be used as a liquid crystal electro-optical element as a liquid crystal composition by being sandwiched between substrates with electrodes.

The liquid crystal composition of the present invention is sandwiched between substrates with electrodes by, for example, being injected into a liquid crystal cell, and is twisted nematic, guest-host, dynamic scattering, phase change, DAP, It can be used in various modes such as a dual frequency drive system and a ferroelectric liquid crystal display system. As a typical liquid crystal electro-optical element, there is a twisted nematic (TN) type liquid crystal electro-optical element. In addition, the term "liquid crystal electro-optical element" is used here to clarify that the liquid crystal electro-optical element can be used not only for display but also for purposes such as a light control window, an optical shutter, a polarization conversion element, and a variable focus lens. is there.

The above liquid crystal electro-optical element can be obtained by the following method. First, 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, if necessary, to form an In ₂ O ₃
After providing electrodes such as SnO ₂ (ITO) and SnO ₂ and patterning, if necessary, an overcoat layer of polyimide, polyamide, SiO ₂ , Al ₂ O ₃ or the like is formed, and alignment treatment is performed. A seal material is printed thereon, the electrodes are arranged so as to face each other, the periphery is sealed, and the seal material is cured to form empty cells. Further, a liquid crystal composition containing the compound (1) of the present invention is injected into the empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, a polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflecting plate, a reflecting plate, a light guide plate, an ultraviolet cut filter, etc. are laminated on this liquid crystal cell, characters and figures are printed, and a non-glare processing is performed. To form a liquid crystal electro-optical element.

The above description describes the basic structure and manufacturing method of the liquid crystal electro-optical element, and other structures can be adopted. For example, a substrate using a two-layer electrode, a two-layer liquid crystal cell having two liquid crystal layers formed thereon, a substrate using a reflective electrode, an active matrix element using an active matrix substrate having an active element such as a TFT or MIM, etc. ,
Various configurations can be used. Further, the above-mentioned TN
Modes other than the liquid crystal display, that is, a high twist angle super twist nematic (STN) type liquid crystal electro-optical element, a guest-host (GH) type liquid crystal electro-optical element using a polychromatic dye, and a liquid crystal molecule in a lateral electric field. In-plane switching (IPS) type liquid crystal electro-optical element for driving liquid crystal molecules parallel to the substrate, VA type liquid crystal electro-optical element for aligning liquid crystal molecules perpendicular to the substrate, ferroelectric liquid crystal electro-optical element, etc. Can be used with In addition, a method in which writing is performed by heat can be used instead of a method in which writing is performed electrically.

As described above, the liquid crystal electro-optical device using the liquid crystal composition containing the compound (1) of the present invention has a low driving voltage, so that the power consumption can be reduced. In particular, when used in an STN-type liquid crystal electro-optical element or the like, the voltage-transmittance characteristic becomes steep, and a liquid crystal electro-optical element with excellent display quality can be obtained. Further, since the liquid crystal composition of the present invention has good compatibility and is chemically stable, an operating temperature range and a storage temperature range are wide, and a highly reliable liquid crystal electro-optical element can be obtained.

[0048]

The present invention will be described more specifically below with reference to examples. [Example 1] 1,4-cyclohexanedimethanol 360.
5 g (2.50 mol) of 47% hydrobromic acid 1750c
dissolved in m ³ and concentrated sulfuric acid 245.2 g (2.50 mol)
Was added and stirred at 80 ° C. for 18 hours. Then, the reaction solution was neutralized with a 25% aqueous sodium hydroxide solution, and MT
After extraction with BE, washing with water and drying, and evaporation of the solvent, distillation under reduced pressure and purification by silica gel column chromatography using 1,2-dichloroethane as a developing solvent were carried out to give 1
137.3 g (yield 27%) of -hydroxymethyl-4- (bromomethyl) cyclohexane was obtained. The obtained 1-
137.3 g (0.663 mol) of hydroxymethyl-4- (bromomethyl) cyclohexane was added to 275 of hexane.
was dissolved in cm ^3, 6.9 g after addition of Amberlyst 15 (Rohm and Haas ion exchange resin), 3,4
66.9 g of dihydro-2H-pyran (0.796 mo
l) was added dropwise. After stirring at room temperature for 4 hours, Amberlyst 15 was removed by filtration, and the solvent was distilled off, followed by silica gel column chromatography using a hexane-toluene mixed solvent to obtain 167.2 g of the following compound (87% yield). .

[0049]

Embedded image 167.2 g (0.574 mol) of this compound was added to THF
The substance dissolved in 502 cm ³ was dropped into a mixture of 17 cm ³ of THF and 15.3 g (0.632 mol) of metallic magnesium with stirring. After stirring at room temperature for 2 hours, the reaction solution was cooled to 0 ° C. and crotyl acetate 65.5 g.
(0.574 mol), 1.04 g (5.74 m) of copper acetate
mol) and THF 852 cm ³ . After the temperature was raised to room temperature, 500 cm ³ of a saturated aqueous solution of ammonium chloride was added, and the mixture was stirred for 10 minutes.
After extraction with TBE, washing with water and drying, the solvent was distilled off to obtain the following compound (147.0 g, yield 96%).

[0050]

Embedded image 147.0 g of this compound was dissolved in 1030 cm ³ of methanol, 7.4 g of Amberlyst 15 was added, and the mixture was refluxed for 3 hours. After cooling to room temperature, Amberlyst 15 was removed by filtration, and after distilling off the solvent, distillation under reduced pressure was performed to obtain the following 1
51.2 g (yield 51%) of -hydroxymethyl-4- (3-pentenyl) cyclohexane was obtained. Boiling point 112 ~
114 ° C / 3mmHg

[0051]

Embedded image 86.5 g of triphenylphosphine (0.330 mo
l) was dissolved in 300 cm ³ of acetonitrile, and bromine 5
After dropping 0.0 g (0.313 mol) at room temperature, the mixture was stirred for 30 minutes. The 1-hydroxymethyl-4- (3-pentenyl) cyclohexane 5 obtained above was added to the reaction solution.
After dropwise adding 0.1 g (0.275 mol), the mixture was stirred at room temperature for 1 hour. After adding 300 cm ^{3 of} water, the mixture was extracted with hexane, washed with water and dried, and the solvent was distilled off. 50.6 g (yield 75%) of cyclohexane was obtained.

[0052]

Embedded image 50.6 g (0.206 mol) of this compound was added to THF2
A solution dissolved in 00 cm ³ was dropped into a mixture of 200 cm ³ of THF, 5.5 g (0.227 mol) of metallic magnesium and a small amount of iodine while stirring at 40 ° C. while confirming heat generation. The mixture was stirred for 2 hours to prepare a Grignard solution.

3,5-difluorobenzyl bromide 3
8.4 g (0.185 mol) of toluene 190 cm ³
After cooling to −30 ° C. and adding 3.5 g (0.0185 mol) of copper iodide, the Grignard solution obtained above was added dropwise while maintaining the temperature. −
After stirring for 2 hours at 30 ° C., the temperature was raised to room temperature, a saturated aqueous solution of ammonium chloride was added, and the mixture was stirred for 1 hour. The crystals were filtered, extracted with toluene, washed with water and dried, and the solvent was distilled off.
39.2 g (yield 65%) of-[2- [4- (3-pentenyl) cyclohexyl] ethyl] benzene was obtained.

[0054]

Embedded image 39.2 g (0.134 mol) of this compound was added to THF2
After dissolving in 00 cm ³ and cooling to −60 ° C., 92 cm ³ of a butyllithium hexane solution (1.6 mol / dm ³ ) was added dropwise. After stirring at −60 ° C. for 2 hours, 10 g of carbon dioxide gas was blown in over 1 hour while maintaining the temperature. After raising the temperature to room temperature, 500 cm ³ of dilute hydrochloric acid was added, and the mixture was stirred for 1 hour, extracted with toluene, washed with water, dried, and the solvent was distilled off. The obtained residue was re-used three times with a hexane-toluene mixed solvent. After crystallization, 2,6-difluoro-4- [2-
[Trans-4- (3-pentenyl) cyclohexyl]
[Ethyl] benzoic acid (21.2 g, yield 47%) was obtained.

[0055]

Embedded image 21.2 g (0.0630 mol) of this compound was dissolved in 85 cm ³ of tetrachloroethylene, and thionyl chloride 2
After adding 2.5 g (0.189 mol) and 0.5 cm ³ of N, N-dimethylaniline and stirring at room temperature overnight, the solvent and excess thionyl chloride were distilled off, and the residue was dissolved in 90 cm ³ of toluene. . This solution was cooled to 10 ° C. with 70 cm ^{3 of} toluene and 18 c of concentrated aqueous ammonia.
m ^{3, and} the mixture was stirred at the same temperature for 1 hour. The precipitated white crystals were filtered, dried, and 2,6-difluoro-4- [2- [trans-4- (3-pentenyl) described below.
Cyclohexyl] ethyl] benzamide (20.1 g, yield 95%) was obtained.

[0056]

Embedded image 20.1 g (0.0600 mol) of this compound was dissolved in 100 cm ³ of toluene, and 17.2 g (0.09 mol) of p-toluenesulfonic acid chloride and pyridine 1
4.2 g (0.18 mol) was added, and the mixture was refluxed for 17 hours. After cooling to room temperature, 200 cm ³ of water was added and the mixture was extracted with toluene, washed with water, washed with an alkali, washed with water and dried, and the solvent was distilled off.The residue was subjected to alumina column chromatography using hexane as a developing solvent. And recrystallized four times to obtain 2,6-difluoro-4- [2-
6.8 g of [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] benzonitrile (yield 36
%). Melting point 55.3 ° C

[0057]

Embedded image The assignments of ¹ H-NMR (CDCl ₃ solvent, TMS standard) spectra are as follows. δ (ppm): 0.79-1.98 (multiplet, aliphatic, 19H), 2.67 (tr
iplet, benzyl, 2H), 5.34-5.48 (multiplet, -CH = CH-, 2H),
6.86 (doublet, aromatic, 2H) The assignment of the ¹⁹ F-NMR (CHCl ₃ , CFCl ₃ standard) spectrum is as follows. δ (ppm): -105.29 (doublet, J _FH = 9.7Hz)

Similarly, the following compounds can be obtained by using the corresponding esters instead of crotyl acetate. 2,6-difluoro-4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (4-pentenyl) cyclohexyl ] Ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- (trans-3-hexenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (5-hexenyl) cyclohexyl] ethyl] benzonitrile, 2,6 -Difluoro-4- [2- [trans-4- (trans-3-
Heptenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-
(Trans-5-heptenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- (2- (vinyloxy) ethyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (2- (allyloxy) ethyl) cyclohexyl] ethyl] benzonitrile , 2,6-difluoro-4- [2- [trans-4-
(2- (trans-2-butenyloxy) ethyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (3- (vinyloxy) propyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-
(3- (allyloxy) propyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- (3- (3-butenyloxy) propyl) cyclohexyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [trans-4- (4-
(Vinyloxy) butyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (4- (allyloxy) butyl) cyclohexyl] ethyl] benzonitrile.

Similarly, the following compounds can be obtained by using the corresponding dimethanol in place of 1,4-cyclohexanedimethanol. 2,6-difluoro-4- [2- [trans-4- [trans-4-
(3-butenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- [trans-4- (trans-3-
Pentenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [trans-4- (trans-3-hexenyl) cyclohexyl] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (5-hexenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [ Trans-4-
[Trans-4- (trans-3-heptenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-5-heptenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [trans-4- [trans-4- (2- (vinyloxy) ethyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (2- (allyloxy) ethyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (2- (trans-2-butenyloxy) ethyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [Trans-4- [trans-4- (3- (vinyloxy) propyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (3 -(Allyloxy) propyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (3- (3-butenyloxy)]
Propyl) cyclohexyl] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (4- (vinyloxy)
Butyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (4- (allyloxy) butyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4 -[2- [trans-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [2- [trans-4- (trans-
3-hexenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-
4- [2- [trans-4- [2- [trans-4-
(5-hexenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4-]
(Trans-3-heptenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [2- [trans-4- (trans-5-heptenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [Trans-4-4
[2- [trans-4- (2- (vinyloxy) ethyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [2- [trans-4- (2- (allyloxy) ethyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2 − [Trans-4-
(2- (trans-2-butenyloxy) ethyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4- (3- (Vinyloxy)
Propyl) cyclohexyl] ethyl] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [2- [trans-4- (3-
(Allyloxy) propyl) cyclohexyl] ethyl]
Cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4- (3- (3-butenyloxy) propyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzo Nitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4- (4- (vinyloxy)
Butyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- [2- [trans-4- (4- (allyloxy) butyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [trans-4- (3-butenyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2 − [Trans-
4- [trans-4- (trans-3-pentenyl) cyclohexylmethyloxy] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-3-hexenyl) cyclohexylmethyloxy] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (5-hexenyl) cyclohexylmethyloxy] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (trans-
3-heptenyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-5-heptenyl) cyclohexylmethyloxy] cyclohexyl] ethyl Benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (2- (vinyloxy) ethyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans -4-
[Trans-4- (2- (allyloxy) ethyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (2- (trans -2-butenyloxy) ethyl) cyclohexylmethyloxy]
Cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4]
-(3- (vinyloxy) propyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-
[Trans-4- (3- (allyloxy) propyl) cyclohexylmethyloxy] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (3- (3-butenyloxy) propyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro -4- [2- [trans-4- [trans-4- (4
-(Vinyloxy) butyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (4- (allyloxy) butyl) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [trans-4- (3-butenyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2 − [Trans-
4- [trans-4- (trans-3-pentenyl) cyclohexyloxymethyl] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-3-hexenyl) cyclohexyloxymethyl] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (5-hexenyl) cyclohexyloxymethyl] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (trans-
3-heptenyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-5-heptenyl) cyclohexyloxymethyl] cyclohexyl] ethyl Benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (2- (vinyloxy) ethyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans -4-
[Trans-4- (2- (allyloxy) ethyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (2- (trans -2-butenyloxy) ethyl) cyclohexyloxymethyl]
Cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4]
-(3- (vinyloxy) propyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-
[Trans-4- (3- (allyloxy) propyl) cyclohexyloxymethyl] cyclohexyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (3- (3-butenyloxy) propyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro -4- [2- [trans-4- [trans-4- (4
-(Vinyloxy) butyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (4- (allyloxy) butyl) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [trans-4- (3-butenyl) cyclohexyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [Trans-4-4
[Trans-4- (trans-3-pentenyl) cyclohexyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4
-[Trans-4- (3-butenyl) cyclohexylmethyl] cyclohexyl] ethyl] benzonitrile, 2,
6-Difluoro-4- [2- [trans-4- [trans-4- (trans-3-pentenyl) cyclohexylmethyl] cyclohexyl] ethyl] benzonitrile.

Similarly, 1-bromomethyl-4- (3
The following compounds can be obtained by using the corresponding methyl bromide derivative instead of (-pentenyl) cyclohexane. 2,6-difluoro-4- [2-
[Trans-4-vinylcyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-allylcyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans -4-
(Trans-1-propenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- (trans-1-butenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (trans-1-pentenyl) cyclohexyl] ethyl] benzonitrile, ,
6-difluoro-4- [2- [trans-4- (trans-1-hexenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (trans-1- to Butenyl) cyclohexyl]
Ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4-vinyloxycyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-allyloxycyclohexyl] ethyl] Benzonitrile, 2,6-difluoro-4- [2- [trans-
4- (trans-1-propenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- (2-propenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (trans-2-
Butenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4
-(Trans-2-pentenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [trans-4- (trans-2-hexenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- (trans-4-hexenyloxy)
Cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (trans-2
-Heptenyloxy) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (trans-4-heptenyloxy) cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [trans-4-vinylcyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [Trans-4-allylcyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-1-propenyl)]
Cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4
-[Trans-4- (trans-1-butenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [trans-4- [trans-4- (trans-1-pentenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [trans-4- [trans-4- (trans-1-hexenyl) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4- (trans-1-heptenyl) cyclohexyl]
Cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [trans-4-vinyloxycyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [trans-4-allyloxycyclohexyl] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (trans-
1-propenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- [trans-4- (2-propenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [trans-4- (trans-2-butenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [trans-4- (trans-2-pentenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- [trans-4- (trans-3-
Pentenyloxy) cyclohexyl] cyclohexyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [trans-4- [trans-4- (trans-
2-hexenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- [trans-4- (trans-2-heptenyloxy) cyclohexyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [2- [trans-4-vinylcyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [Trans-4-4
[2- [trans-4-allylcyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [2- [trans-4- (trans-1-propenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [Trans-4-4
[2- [trans-4- (trans-1-butenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4-] (Trans-1-pentenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- [2- [trans-4- (trans-1-hexenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2 − [Trans-4-
(Trans-1-heptenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- [2- [trans-4-vinyloxycyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2 − [Transformer-4
-[2- [trans-4-allyloxycyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4-
[2- [trans-4- (trans-1-propenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- [2- [trans-4- (2-propenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- [2- [trans-4- (trans-2-butenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [2- [trans-4- (trans-2-pentenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2 -[Trans-4- [2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- [2- [trans-4- (trans-2-hexenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6
-Difluoro-4- [2- [trans-4- [2- [trans-4- (trans-2-heptenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- (4-vinylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[Trans-4- (4-allylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- (4- (3-butenyl) phenyl) cyclohexyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [trans-4- (4-
(Trans-3-pentenyl) phenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [trans-4- (2,6-difluoro-4-
Vinylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4
-(2,6-difluoro-4-allylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (2,6-difluoro-4- (3-butenyl)] Phenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[Trans-4- (2,6-difluoro-4- (trans-3-pentenyl) phenyl) cyclohexyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [trans-4- (2-fluoro-4-vinylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans- 4- (2-fluoro-4-
Allylphenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4
-(2-Fluoro-4- (3-butenyl) phenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- (2-fluoro-
4- (trans-3-pentenyl) phenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4- (trans-4-vinylcyclohexyl) phenyl] ethyl] benzonitrile, 2,6 -Difluoro-4- [2- [4- (trans-4-allylcyclohexyl) phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [4- [trans-4
-(Trans-3-pentenyl) cyclohexyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-
4- [2- [4- [trans-4- (3-butenyl) cyclohexyl] phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [2,6
-Difluoro-4- (trans-4-vinylcyclohexyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- (trans-4-allylcyclohexyl) phenyl] Ethyl] benzonitrile, 2,6-difluoro-4- [2-
[2,6-difluoro-4- [trans-4- (trans-3-pentenyl) cyclohexyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[2,6-difluoro-4- [trans-4- (3-butenyl) cyclohexyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- (trans-4 -Vinylcyclohexyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-
4- [2- [2-fluoro-4- (trans-4-allylcyclohexyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-
4- [trans-4- (trans-3-pentenyl) cyclohexyl] phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [2-fluoro-4-
[Trans-4- (3-butenyl) cyclohexyl] phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [4-
[2- (trans-4-vinylcyclohexyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4- [2- (trans-4-allylcyclohexyl) ethyl] phenyl] ethyl ] Benzonitrile, 2,6-difluoro-4- [2- [4- [2
-[Trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4- [2- [trans-4- (3-butenyl) ) Cyclohexyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
(Trans-4-vinylcyclohexyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-
4- [2- [2,6-difluoro-4- [2- (trans-4-allylcyclohexyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[2,6-difluoro-4- [2- [trans-4-
(Trans-3-pentenyl) cyclohexyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
[Trans-4- (3-butenyl) cyclohexyl] ethyl] phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [2-fluoro-4- [2- (trans-4-vinylcyclohexyl) ethyl] phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [2-fluoro-4-
[2- (trans-4-allylcyclohexyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- [2- [trans-4- (trans-3 -Pentenyl) cyclohexyl] ethyl] phenyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [2-fluoro-4- [2
-[Trans-4- (3-butenyl) cyclohexyl]
Ethyl] phenyl] ethyl] benzonitrile, 2,6-
Difluoro-4- [2- (4-vinylphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2-
(4-vinyloxyphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (4-allylphenyl) ethyl] benzonitrile, 2,6-difluoro-
4- [2- [4- (trans-3-pentenyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [4- (3-butenyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4-
(Trans-3-pentenyloxy) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[4- (3-Butenyloxy) phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- (2,6
-Difluoro-4-vinylphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (2,6-difluoro-4-vinyloxyphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (2,6-
Difluoro-4-allylphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- (trans-3-pentenyl) phenyl]
Ethyl] benzonitrile, 2,6-difluoro-4-
[2- [2,6-difluoro-4- (trans-3-pentenyloxy) phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [2,6-difluoro-4- (3-butenyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro- 4- (3-butenyloxy) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
(2-Fluoro-4-vinylphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (2-fluoro-4-vinyloxyphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (2-fluoro-4-allylphenyl) ethyl] benzonitrile, 2,
6-difluoro-4- [2- [2-fluoro-4- (trans-3-pentenyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- (3 -Butenyl) phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- (trans-3-pentenyloxy) phenyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [2-Fluoro-4- (3-butenyloxy)
[Phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [4-
[2- (4-vinylphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[4- [2- (4-vinyloxyphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4- [2- (4-allylphenyl) ethyl] phenyl] ethyl ] Benzonitrile, 2,6-difluoro-4- [2- [4- [2- [4- (trans-3
-Pentenyl) phenyl] ethyl] phenyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [4
-[2- [4- (3-butenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [4- [2- [4- (trans-3-pentenyloxy) ) Phenyl] ethyl] phenyl] ethyl]
Benzonitrile, 2,6-difluoro-4- [2- [4
-[2- [4- (3-butenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
(4-vinylphenyl) ethyl] phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [2,6
-Difluoro-4- [2- (4-vinyloxyphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,
6-difluoro-4- [2- [2,6-difluoro-4
-[2- (4-allylphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2
-[2,6-difluoro-4- [2- [4- (trans-3-pentenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[2,6-difluoro-4- [2- [4- (3-butenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4 -[2- [4- (trans-3-pentenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-
Difluoro-4- [2- [4- (3-butenyloxy)
[Phenyl] ethyl] phenyl] ethyl] benzonitrile.

2,6-difluoro-4- [2- [2-fluoro-4- [2- (4-vinylphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-Fluoro-4- [2- (4-vinyloxyphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- [2- (4- Allylphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4
-[2- [2-fluoro-4- [2- [4- (trans-3-pentenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2-
[2-fluoro-4- [2- [4- (3-butenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [2-fluoro-4-
[2- [4- (trans-3-pentenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile,
2,6-difluoro-4- [2- [2-fluoro-4-
[2- [4- (3-butenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
(2,6-difluoro-4-vinylphenyl) ethyl]
Phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
(2,6-difluoro-4-vinyloxyphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2
-(2,6-difluoro-4-allylphenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
[2,6-difluoro-4- (trans-3-pentenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2- [2,6-difluoro-4- (3-
Butenyl) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6
-Difluoro-4- [2- [2,6-difluoro-4-
(Trans-3-pentenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2-
[2,6-Difluoro-4- (3-butenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile.

Similarly, the following compound can be obtained by using trans-4- (3,5-difluorophenyl) cyclohexylmethyl bromide instead of 3,5-difluorobenzyl bromide. 2,6
-Difluoro-4- [trans-4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4
-[Trans-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [trans-4- (3-butenyloxy) cyclohexyl] ethyl] cyclohexyl]
Benzonitrile, 2,6-difluoro-4- [trans-4- [2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [ Trans-4- [2- [4- (trans-3-pentenyl)
Phenyl] ethyl] cyclohexyl] benzonitrile,
2,6-difluoro-4- [trans-4- [2- [4
-(3-butenyl) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [4- (trans-3-pentenyloxy) phenyl] ethyl] cyclohexyl] benzonitrile , 2,6-difluoro-4- [trans-4- [2
-[4- (3-butenyloxy) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-
4- [trans-4- [2- [2,6-difluoro-4]
-(Trans-3-pentenyl) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-
4- [trans-4- [2- [2,6-difluoro-4]
-(3-Butenyl) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2,6-difluoro-4- (trans-3-pentenyloxy) phenyl] Ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [2,6-difluoro-4-
(3-Butenyloxy) phenyl] ethyl] cyclohexyl] benzonitrile.

2,6-difluoro-4- [trans-4
-[2- [2-fluoro-4- (trans-3-pentenyl) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2
-[2-Fluoro-4- (3-butenyl) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2-fluoro-
4- (trans-3-pentenyloxy) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2-fluoro-
4- (3-butenyloxy) phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [trans-4- [trans-
4- (3-butenyl) cyclohexyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6
-Difluoro-4- [trans-4- [2- [trans-4- [trans-4- (trans-3-pentenyl)]
Cyclohexyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [trans-4- [trans-4-]
(3-butenyloxy) cyclohexyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6
-Difluoro-4- [trans-4- [2- [trans-4- [trans-4- (trans-3-pentenyloxy) cyclohexyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile.

2,6-difluoro-4- [trans-4
-[2- [trans-4- [2- [trans-4- (3
-Butenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6
-Difluoro-4- [trans-4- [2- [trans-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6- Difluoro-4- [trans-4- [2- [trans-4-
[2- [trans-4- (3-butenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [trans-4- [2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] cyclohexyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [4- [trans-4- (3-
Butenyl) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [4- [trans-4- (trans-3-pentenyl) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [4- [trans-4- (3-butenyloxy) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6
-Difluoro-4- [trans-4- [2- [4- [trans-4- (trans-3-pentenyloxy) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile.

2,6-difluoro-4- [trans-4
-[2- [4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4
-[Trans-4- [2- [4- [2- [trans-4
-(Trans-3-pentenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2-
[4- [2- [trans-4- (3-butenyloxy)
Cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4-
[Trans-4- [2- [4- [2- [trans-4-
(Trans-3-pentenyloxy) cyclohexyl]
Ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4-
[2- [2,6-difluoro-4- [trans-4-
(3-butenyl) cyclohexyl] phenyl] ethyl]
Cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2,6-difluoro-
4- [trans-4- (trans-3-pentenyl) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-
4- [2- [2,6-difluoro-4- [trans-4
-(3-butenyloxy) cyclohexyl] phenyl]
Ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2,6-difluoro-4- [trans-4- (trans-3-pentenyloxy) cyclohexyl] phenyl] ethyl ] Cyclohexyl] benzonitrile.

2,6-difluoro-4- [trans-4
-[2- [2,6-difluoro-4- [2- [trans-4- (3-butenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,
6-difluoro-4- [trans-4- [2- [2,6
-Difluoro-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6
-Difluoro-4- [trans-4- [2- [2,6-
Difluoro-4- [2- [trans-4- (3-butenyloxy) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2,6 -Difluoro-4- [2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2-fluoro-
4- [trans-4- (3-butenyl) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2-
[2-fluoro-4- [trans-4- (trans-3
-Pentenyl) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-
4- [trans-4- [2- [2-fluoro-4- [trans-4- (3-butenyloxy) cyclohexyl]]
Phenyl] ethyl] cyclohexyl] benzonitrile,
2,6-difluoro-4- [trans-4- [2- [2
-Fluoro-4- [trans-4- (trans-3-pentenyloxy) cyclohexyl] phenyl] ethyl]
Cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [2-fluoro-4-
[2- [trans-4- (3-butenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4
-[2- [2-fluoro-4- [2- [trans-4-
(Trans-3-pentenyl) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2-
[2-Fluoro-4- [2- [trans-4- (3-butenyloxy) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile, 2,6-difluoro-4- [trans-4- [2- [ 2-fluoro-
4- [2- [trans-4- (trans-3-pentenyloxy) cyclohexyl] ethyl] phenyl] ethyl] cyclohexyl] benzonitrile.

Example 2 A liquid crystal composition “ZLI-” manufactured by Merck & Co., Ltd.
1565 "(nematic-isotropic phase transition point, N-
I) was 85.9 ° C. A TN type liquid crystal cell having a substrate interval of 8.0 μm was formed by forming a silicon oxide coat layer on a substrate with an ITO electrode and sandwiching the liquid crystal composition between rubbed substrates. The threshold voltage of this liquid crystal cell at 25 ° C. was measured.
It was 41V.

Example 3 A liquid crystal composition “ZLI-” manufactured by Merck & Co., Ltd.
1565 "to 80 wt% of [2,6-difluoro-4- [2- [trans-4- (trans-3) synthesized in Example 1.
-Pentenyl) cyclohexyl] ethyl] benzonitrile] was added in an amount of 20 wt%. The clearing point (NI) of this liquid crystal composition was 62.8 ° C. Using this liquid crystal composition, a TN type liquid crystal cell was prepared in the same manner as in Example 2. The threshold voltage of this liquid crystal cell at 25 ° C. was 1.4.
The driving voltage was 4 V, which was much lower than that of the liquid crystal cell of Example 2.

Example 4 A liquid crystal composition “ZLI-” manufactured by Merck & Co., Ltd.
2293 "had a clearing point (NI) of 84.4 ° C.
Forming a coat layer of silicon oxide on a substrate with ITO electrodes,
An STN-type liquid crystal cell having a substrate spacing of 6.5 μm was formed by sandwiching the liquid crystal composition between the rubbed substrates. The measured threshold voltage of this liquid crystal cell at 25 ° C. was 2.16 V. The ratio γs (= V ₁₀ / V ₉₀ ) between the voltage V _{10 at} which the transmittance in the normal direction changes by 10% and the voltage V _{90 at} which the transmittance changes by 90% is 0.912.
Met.

Example 5 A liquid crystal composition “ZLI-” manufactured by Merck & Co., Ltd.
2293 "to 80 wt% of [2,6-difluoro-4- [2- [trans-4- (trans-3
-Pentenyl) cyclohexyl] ethyl] benzonitrile] was added in an amount of 20 wt%. The clearing point (NI) of this liquid crystal composition was 61.2 ° C. Using this liquid crystal composition, an STN type liquid crystal cell was prepared in the same manner as described above. The threshold voltage of the liquid crystal cell was 1.35 V, and the drive voltage was significantly lower than that of the liquid crystal cell of Example 4. In addition, γs is set to 0.
920, indicating that the voltage-transmittance characteristic was steeper than that of the liquid crystal cell of Example 4.

[0088]

As described above, the compound (1) of the present invention has a very large positive dielectric anisotropy, and the liquid crystal optical element using the liquid crystal composition containing the compound (1) has a low voltage. And display quality is excellent. In addition, since the compatibility in the liquid crystal composition is good and the composition is chemically stable, a liquid crystal electro-optical element having a wide operating temperature range and a storage temperature range and high reliability can be obtained. This compound (1) can be easily produced industrially according to the production method of the present invention, and the intermediate compound (2) can also be suitably used for a liquid crystal electro-optical element.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 19/20 C09K 19/20 19/30 19/30 G02F 1/13 500 G02F 1/13 500 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Takeshi Koike 3-2-10 Chigasaki, Chigasaki-shi, Kanagawa F-term in Seimi Chemical Co., Ltd. (Reference) 4H006 AA01 AA02 AB64 AC22 AC54 BA05 BA37 BD70 QN20 4H027 BA01 BB03 BD01 BD02 BD05 BD10 BD24 CB04 CE04 CH04 CK04 CN04 CR04 CU04 4H039 CA41 CD20 CD90

Claims (8)

[Claims] 1. A difluorobenzonitite represented by the formula (1)
Ryl compounds. Embedded imageHowever, the symbols in the formula (1) have the following meanings (only
A^TwoIs an unsubstituted 1,4-phenylene group, and q is
A is 1, when Y is a single bond, and r is 0,¹
Is not an unsubstituted 1,4-phenylene group). R: an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom. -CH = CH-: a trans-vinylene group. X: oxygen atom or single bond. A¹, A^Two: Independently of each other, 1,4-phenylene group
Or a trans-1,4-cyclohexylene group. A¹And
And A^TwoGroups are each unsubstituted or substituted
And one or more halogen atoms or methyl groups
May have, A¹And A^Two1 existing in the group of
One or more CH groups are replaced by nitrogen atoms
Or one or more CH_TwoThe group is an oxygen atom or
May be substituted by a sulfur atom. A^Three: A trans-1,4-cyclohexylene group or
1,4-phenylene group. A^ThreeIs trans-1,4-sig
In the case of a rohexylene group, this group may be unsubstituted or
Represents one or more halogen atoms as substituents or
May have a methyl group, and up to one
Or two or more CH groups may be substituted with a nitrogen atom
One or more CH_TwoThe group is an oxygen atom or sulfur
It may be substituted by a yellow atom. A^ThreeIs 1,4-phenyl
In the case of a benzene group, this group may be substituted by one or more
Having the above halogen atom or methyl group,
One or more existing CH groups are replaced with nitrogen atoms
It may be. Y: -CH_TwoCH_Two-, -CH_Two-, -CH = CH-,
-OCH_Two-, -CH _TwoO-, -O-, -CF = CF
-, -C≡C- or a single bond. m, n: 0, 1, 2, 3 or 4 independently of each other. q, r: 0 or 1 independently of each other. 2. The difluorobenzonitrile compound according to claim 1, wherein r is 0. 3. The difluorobenzonitrile compound according to claim 1, wherein r is 0 and A ² is an unsubstituted trans-1,4-cyclohexylene group. 4. A difluorobenzene compound represented by the formula (2)
Compound. Embedded imageHowever, the symbols R, X, A in the formula (2)¹, A^Two, A^Three,
Y, m, n, q and r are the same as in the formula (1)
Indicates meaning (however, A^TwoIs unsubstituted 1,4-phenylene
Q is 1, Y is a single bond, and r
Is 0, A ¹Is an unsubstituted 1,4-phenylene group
Absent). 5. A method of reacting a compound represented by the formula (3) with magnesium metal to obtain a Grignard reagent, followed by reacting the compound represented by the formula (4) with a transition metal catalyst. A method for producing a difluorobenzene compound according to claim 4. Embedded image However, the symbols R, X, A ¹ ,
A ² , A ³ , Y, m, n, q and r have the same meanings as in the formula (1), and B ¹ and B ² have the following meanings. B ¹ : chlorine atom, bromine atom or iodine atom. B ² : a leaving group. 6. A Grignard reagent obtained by reacting a compound represented by the formula (3) with magnesium metal, and then reacting with a compound represented by the formula (4) in the presence of a transition metal catalyst. The method for producing a difluorobenzonitrile compound according to any one of claims 1 to 3, wherein the method passes through a step of synthesizing the compound represented by (2). 7. A liquid crystal composition comprising at least one difluorobenzonitrile compound according to claim 1. 8. A liquid crystal electro-optical element comprising the liquid crystal composition according to claim 7 sandwiched between substrates with electrodes.