JP4573399B2 - Difluorobenzonitrile compound and intermediate thereof, production method, liquid crystal composition, and liquid crystal electro-optical element - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a difluorobenzonitrile compound used for a liquid crystal electro-optical element and an intermediate thereof, a liquid crystal composition containing the compound, and a liquid crystal electro-optical element using the liquid crystal composition.
[0002]
[Prior art]
Liquid crystal electro-optical elements using liquid crystal materials are used in various applications such as display devices for office automation equipment, portable devices, home appliances, watches, calculators, measuring instruments, automotive instruments, copying machines, cameras, etc. There are various performance requirements such as a wide operating temperature range, a low operating voltage, high-speed response, and chemical stability.
However, at present, there is no compound that satisfies all of these characteristics alone, and the required performance as a liquid crystal composition by mixing one or more liquid crystal compounds and / or non-liquid crystal compounds with excellent characteristics. Meet.
[0003]
Among various properties required for liquid crystal compounds in the field of display elements using liquid crystals, it has excellent compatibility with other liquid crystal materials or non-liquid crystal materials, is chemically stable, and is used in liquid crystal electro-optical elements. It is an important issue to provide a compound having such a property that it can be driven at a low voltage when used.
As solutions for such problems, the following difluorobenzonitrile compounds are disclosed.
(I), (ii): Japanese Patent Laid-Open No. 62-103057
(Iii): JP-A-1-131144
(Iv): Japanese Patent Laid-Open No. 3-130253
[0004]
[Formula 4]
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, demands for viewing angle characteristics, low voltage drivability, contrast, and visibility have become more severe, and development of compounds that can further improve display quality while maintaining low voltage drivability in liquid crystal electro-optic elements. Is expected.
[0005]
[Problems to be solved by the invention]
An object of the present invention is 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 contained therein.
[0006]
[Means for Solving the Problems]
As a result of various investigations focusing on a compound having an alkenyl group and a difluorobenzonitrile group, the present inventors have made a liquid crystal composition having a specific structure among those having these groups. When it is contained, the present inventors have found that 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, thereby completing the present invention.
[0007]
By the way, although JP-A-4-296387 discloses a formula including a difluorobenzonitrile compound having an alkenyl group, a description of a specific compound name or a physical name of the difluorobenzonitrile compound having an alkenyl group is provided. There is no description of data, liquid crystal properties, etc., nor is it described the effect of having an alkenyl group.
In addition, in a conventionally known production method (for example, the production method described in JP-A-62-13057, JP-A-1-131144, or JP-A-3-130253), a terminal group is known. In the case of a compound having a double bond such as an alkenyl group, it cannot be easily produced due to the reactivity of the double bond in the terminal group.
[0008]
The present invention provides a difluorobenzonitrile compound represented by the formula (1) (hereinafter also referred to as “compound (1)”).
[Chemical formula 5]
However, symbols in the formulas have the following meanings throughout this specification.
R: an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom.
-CH = CH-: trans-vinylene group.
X: an oxygen atom or a single bond.
A¹, A²: Independently from each other, a 1,4-phenylene group or a trans-1,4-cyclohexylene group. A¹And A²Each of the groups may be unsubstituted or may have one or more halogen atoms or methyl groups as substituents.¹And A²One or two or more CH groups present in the group may be substituted with a nitrogen atom, and one or two or more CH groups may be substituted.₂The group may be substituted with an oxygen atom or a sulfur atom.
A^Three: Trans-1,4-cyclohexylene group or 1,4-phenylene group.
A^ThreeIs a trans-1,4-cyclohexylene group, this group may be unsubstituted or may have one or more halogen atoms or methyl groups as substituents and is present in the group One or more CH groups may be substituted with nitrogen atoms, and one or more CH groups₂The group may be substituted with an oxygen atom or a sulfur atom.
A^ThreeIs a 1,4-phenylene group, this group has one or more halogen atoms or methyl groups as substituents, and one or more CH groups present in the group are nitrogen An atom may be substituted.
Y: -CH₂CH₂-, -CH₂-, -CH = CH-, -OCH₂-, -CH₂O—, —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, A²Is an unsubstituted 1,4-phenylene group, q is 1, Y is a single bond, and r is 0, A¹Is not an unsubstituted 1,4-phenylene group.
In the formula (1), r is preferably 0. R is 0, and A²Is preferably an unsubstituted trans-1,4-cyclohexylene group.
[0009]
In addition, the present invention 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]
[Chemical 6]
[0011]
In the present invention, a compound represented by formula (3) is reacted with metallic magnesium to form a Grignard reagent, and then reacted with the compound represented by formula (4) in the presence of a transition metal catalyst. A method for producing a difluorobenzene compound represented by the characteristic formula (2) is provided.
[0012]
[Chemical 7]
However, symbols in the formulas have the following meanings throughout this specification.
B¹: Chlorine atom, bromine atom or iodine atom.
B²: A leaving group.
Moreover, this invention provides the manufacturing method of the difluoro benzonitrile compound of Formula (1) characterized by passing through said manufacturing process.
The present invention also provides a liquid crystal composition containing one or more difluorobenzonitrile compounds of the formula (1), and further a liquid crystal electro-optical element obtained by sandwiching the liquid crystal composition between substrates with electrodes.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The compound represented by formula (1) of the present invention is a difluorobenzonitrile compound having an alkenyl group (hereinafter, the compound represented by formula (1) is also referred to as compound (1)).
[0014]
In the compound (1), R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom. Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include linear or branched alkyl groups having 1, 2, 3, 4 or 5 carbon atoms. In particular, the compatibility is high and T_cIs preferred, a linear alkyl group or a hydrogen atom is preferred.
X is an oxygen atom or a single bond. M and n are each independently 0, 1, 2, 3 or 4. When X is an oxygen atom, m + n is preferably 1 or 3.
When X is a single bond, m + n is preferably 0, 2 or 4. X is preferably a single bond because the viscosity is low.
[0015]
In the compound (1), R—CH═CH— (CH)_m-X- (CH)_n-(Hereinafter also referred to as terminal group Z) is preferably a group as shown below.
The terminal group Z in which X is a single bond includes 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-5-heptenyl group, trans-3-heptenyl group, trans-1-heptenyl group 7-octenyl group, trans-5-octenyl group, trans-3-octenyl group, and trans-1-octenyl group are preferable.
As the terminal group Z in which X is an oxygen atom, 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-butyl Tenenyloxymethyl 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-he Cenyloxymethyl 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, 3 -(Allyloxy) propyl group, 3- (1-propenyloxy) propyl group, 3- (3-butenyloxy) propyl group, 3- (trans-1-butenyloxy) propyl group, 4- (vinyloxy) butyl group, 4- (Allyloxy) butyl group and 4- (1-propenyloxy) butyl group are preferred.
[0016]
A¹, A²Are independently of each other a 1,4-phenylene group or a trans-1,4-cyclohexylene group. A¹And A²Each of the groups may be unsubstituted or may have one or more halogen atoms or methyl groups as substituents.¹And A²One or two or more CH groups present in the group may be substituted with a nitrogen atom, and one or two or more CH groups may be substituted.₂The group may be substituted with an oxygen atom or a sulfur atom. When it has a halogen atom as a substituent, the value of Δε is further increased. As the halogen atom, a fluorine atom is preferable because of its low viscosity. In addition, the position of these substituents is not limited.
[0017]
A¹, A²As, for example, unsubstituted 1,4-phenylene group, unsubstituted trans-1,4-cyclohexylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene Group, 2,5-pyrimidinylene group, 2,5-pyridinylene group, 3-methyl-1,4-phenylene group, 1,3-dioxane-2,5-diyl group and the like. In this specification, A¹, A²And A^ThreeThe positions of the 1-position and 4-position of the group of are always the 1-position closer to R in the formula (1).
[0018]
A^ThreeIs a trans-1,4-cyclohexylene group or a 1,4-phenylene group. A^ThreeIs a trans-1,4-cyclohexylene group, this group may be unsubstituted or may have one or more halogen atoms or methyl groups as substituents.^ThreeOne or two or more CH groups present in the group may be substituted with a nitrogen atom, and one or two or more CH groups may be substituted.₂The group may be substituted with an oxygen atom or a sulfur atom. A^ThreeIs a 1,4-phenylene group, this group has one or more halogen atoms or methyl groups as substituents, and one or more CH groups present in the group are It may be substituted with a nitrogen atom. If it has a halogen atom, the same effect as described above is expected. In addition, the position of these substituents is not limited. A^ThreeAs, for example, unsubstituted trans-1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1, Examples include 4-phenylene group and 3-methyl-1,4-phenylene group. Among these, an unsubstituted trans-1,4-cyclohexylene group is preferable from the viewpoint of decreasing the viscosity and improving the liquid crystallinity, and the value of Δε increases, and the driving voltage of the liquid crystal electro-optical element is lowered. In view of the above, a 3-fluoro-1,4-phenylene group or a 3,5-difluoro-1,4-phenylene group is preferable.
[0019]
Y is -CH₂CH₂-, -CH₂-, -CH = CH-, -OCH₂-, -CH₂O—, —O—, —CF═CF—, —C≡C— or a single bond. Of these, -CH₂CH₂-, -OCH₂-, -CH₂O—, —C≡C—, and a single bond are preferable from the viewpoint of liquid crystallinity.
q and r are 0 or 1 independently of each other. When importance is attached to low viscosity, r is preferably 0. q is preferably 0 from the viewpoint of low viscosity. In particular, r is 0 and A²A compound in which is an unsubstituted trans-1,4-cyclohexylene group has a lower viscosity and is preferable.
[0020]
Hereinafter, suitable examples of the compound (1) will be shown by classifying 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. Also, “-Ph^FFCN ”represents 3,5-difluoro-4-cyanophenyl group (the following formula (v)),“ —Ph^FF“−” Represents a 3,5-difluoro-1,4-phenylene group (the following formula (vi)), “—Ph”.^F“-” Represents a 3-fluoro-1,4-phenylene group (the following formula (vii)).
[0021]
[Chemical 8]
[0022]
R in the formula (1) is 0, and A²Specific examples of the compound in which is an unsubstituted trans-1,4-cyclohexylene group include the following compounds. Among these, the bicyclic compound has a particularly low viscosity and is suitable for increasing the response speed of the liquid crystal electro-optical element. Tricyclic compounds exhibit liquid crystal properties 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- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-OCH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-OCH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-OCH₂-Cy-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-OCH₂-Cy-CH₂CH₂-Ph^FFCN
[0023]
Among the compounds in which r in Formula (1) is 0, A²Specific examples of the compound in which is an unsubstituted 1,4-phenylene group include the following compounds. Of these, tricyclic compounds exhibit liquid crystal properties 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- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-OCH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-OCH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-OCH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-OCH₂-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph -C≡C-Ph-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph -C≡C-Ph-CH₂CH₂-Ph^FFCN
[0024]
In the compound where r in Formula (1) is 0, A¹And A²Or A¹And A²Are both 3-fluoro-1,4-phenylene groups or 3,5-difluoro-1,4-phenylene groups, the compounds shown in the specific examples below have a larger Δε value, It is suitable for lowering the driving voltage of the optical element.
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O- Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O- Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O- Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O- Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O- Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O- Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^F-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^F-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^F-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^F-CH₂CH₂-Ph^F-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-CH₂CH₂-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^F-CH₂O-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^F-CH₂O-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-CH₂O-Ph^FF-CH₂CH₂-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-CH₂O-Ph^FF-CH₂CH₂-Ph^FFCN
[0025]
Further, among the compounds (1), the compound in which r is 1 specifically includes the following compounds. Among these, tricyclic compounds exhibit liquid crystal properties up to a relatively high temperature range, and are suitable compounds for driving a liquid crystal electro-optical element in a wide temperature range. Further, the tetracyclic compound exhibits liquid crystallinity up to a higher temperature range and is a suitable compound for driving the liquid crystal electro-optical element in the higher temperature range.
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Cy-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Cy-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-Ph-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Ph-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-Cy-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Cy-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂CH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-CH₂O-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂O-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-OCH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-OCH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-OCH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-OCH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-OCH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-OCH₂-Ph-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-OCH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-OCH₂-Cy-CH₂CH₂-Cy-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph -C≡C-Ph-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph -C≡C-Ph-CH₂CH₂-Cy- Ph^FFCN
[0026]
Moreover, r is 1 among compounds (1), and A¹, A²And A^ThreeThe compounds as shown in the following specific examples in which one or two or more of them are a 3-fluoro-1,4-phenylene group or a 3,5-difluoro-1,4-phenylene group have relatively high Liquid crystallinity is exhibited up to the temperature range, and the value of Δε is further increased, which is suitable for lowering the driving voltage of the liquid crystal electro-optical element.
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph^F-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^F-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^F-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^F-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-CH₂CH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-CH₂CH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph^FF-CH₂O-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF -CH₂O- Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂O- Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂O- Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-OCH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-OCH₂-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Ph -C≡C-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph -C≡C-Ph^FF-CH₂CH₂-Cy- Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^F-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-CH₂CH₂-Ph^FF -Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph^F-Ph^FFCN
  R-CH = CH- (CH₂)_{m + n}-Ph-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph-CH₂CH₂-Ph^F-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph-CH₂CH₂-Ph^FF -Ph^FFCN
R-CH = CH- (CH₂)_m-O- (CH₂)_n-Cy-Ph-CH₂CH₂-Ph^FF -Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Cy-CH₂CH₂-Ph^F-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph-Cy-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Cy-CH₂CH₂-Ph^F-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Cy-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^F-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Ph^FF-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^F-CH₂CH₂-Ph^FF-Ph^FFCN
R-CH = CH- (CH₂)_{m + n}-Cy-Ph^FF-CH₂CH₂-Ph^FF-Ph^FFCN
In the above description, A¹And A²Specific examples in the case where is a 1,4-phenylene group or a trans-1,4-cyclohexylene group are given below.¹And A²A compound substituted with 2,5-pyrimidinylene group, 2,5-pyridinylene group, 1,3-dioxane-2,5-diyl group, 3-methyl-1,4-phenylene group or the like is also appropriately selected. Similarly A^ThreeA compound in which is substituted with a 1,3-dioxane-2,5-diyl group or the like is also appropriately selected.
[0027]
Compound (1) can be easily produced industrially according to the following method.
[Chemical 9]
That is, a Grignard reagent is obtained by reacting the compound represented by the formula (3) with magnesium metal. In equation (3), B¹Represents a chlorine atom, a bromine atom or an iodine atom, but from the viewpoint of reactivity and stability, B¹Is preferably a bromine atom. As the solvent, ether solvents are preferable, and tetrahydrofuran (THF) or t-butyl methyl ether (MTBE) is particularly preferable industrially.
The obtained Grignard reagent is reacted with a compound of formula (4) in the presence of a transition metal catalyst to give a compound of formula (2). In equation (4), B²May be any group having a property of being eliminated during the reaction, and is appropriately selected depending on the reaction conditions and the type of catalyst. Of these, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, an acetoxy group, a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group is preferable, and a bromine atom or p- A toluenesulfonyloxy group is particularly preferred.
As the transition metal catalyst, a copper-based compound, particularly copper (I) iodide, copper (I) cyanide, copper (II) acetate and the like are preferable 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. It is also effective and preferable to use a hydrocarbon solvent such as toluene or hexane in order to suppress side reactions. The reaction temperature varies depending on the leaving group, the catalyst used, and the solvent, but is preferably about −100 ° C. to + 100 ° C., particularly preferably about −50 ° C. to + 30 ° C.
[0028]
There are various methods for obtaining the compound (1) from the obtained compound (2), but industrially, for example, it can be produced by the following method.
That is, the compound (2) is lithiated with a lithiating agent and then reacted with carbon dioxide gas to obtain a carboxylic acid compound of the formula (7). As the lithiating agent, butyl lithium is preferable 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 preferably about −100 ° C. to 0 ° C., particularly preferably about −70 ° C. to −20 ° C., depending on the lithiating agent and solvent used.
[0029]
The obtained carboxylic acid (7) is halogenated with a halogenating agent to give an acid halide (8). As the halogenating agent, thionyl chloride, oxalyl chloride and the like are preferred industrially. A catalyst may or may not be added, but it is also effective and preferable to add N, N-dimethylaniline, triethylamine, pyridine or the like as a catalyst. The reaction may be solventless or use a solvent, but it is preferable to use tetrachloroethylene, dichloromethane, dichloroethane or the like as a solvent from the viewpoint of workability. The reaction temperature is preferably about 0 ° C. to 100 ° C., depending on the presence of the catalyst and the solvent.
The obtained acid halide (8) is reacted with ammonia or an amine to give an acid amide (9). The reactant is industrially preferably ammonia. The reaction may be solventless or use a solvent, but it is preferable to use toluene or the like as a solvent from the viewpoint of workability.
Alternatively, the carboxylic acid (7) can be directly amidated with an amidating agent to give an acid amide (9).
[0030]
The target compound (1) can be obtained by reacting the acid amide (9) thus obtained with a dehydrating agent. As the dehydrating agent, thionyl chloride or paratoluenesulfonic acid chloride-pyridine is preferable. Although various solvents can be used as the reaction solvent, toluene and the like are preferred industrially. The reaction temperature depends on the dehydrating agent and solvent used, but is preferably about 0 ° C to 200 ° C, particularly preferably about 50 ° C to 150 ° C.
Alternatively, the target compound (1) can also be obtained by lithiating the compound (2) with a lithiating agent and then directly reacting with the cyanogen compound. Examples of cyanogen compounds include dicyan and chlorocyan.
[0031]
The manufacturing method of the compound (3) used by reaction is not specifically limited, It can manufacture by the method used normally. For example, it can be produced according to the following synthesis route.
1. A¹= 1,4-phenylene group, q = 1, n = 1 to 3
Embedded image
Compound (a) is dissolved in a solvent such as hexane, and stirred with 3,4-dihydro-2H-pyran in the presence of Amberlyst 15 (Rohm & Haas ion exchange resin) as a catalyst. b) is obtained. Next, the compound (c) is dissolved in THF, and a solution of metal magnesium in THF is added dropwise thereto. After stirring for about 2 hours, the reaction solution was cooled, and the reaction solution was combined with compound (b) and Ni (dppe)₂Cl₂In the solvent. The mixture is warmed to room temperature, saturated aqueous ammonium chloride solution is added and stirred for about 10 minutes, and then the crystals are filtered and extracted with MTBE to obtain compound (d). This compound (d) is refluxed in a solvent such as methanol in the presence of Amberlyst 15 to obtain compound (e). Next, triphenylphosphine (PPh_Three) Is dissolved in acetonitrile, bromine is added dropwise thereto, and the compound (e) is added dropwise to the reaction solution stirred for about 30 minutes, followed by stirring for about 1 hour. The resulting reaction product is purified to obtain compound (3- (1)).
[0032]
2. A²= 1,4-phenylene group, q = 0, n = 1 to 3
Embedded image
The compound (3- (2)) can be obtained in the same manner as in 1.
[0033]
3. A¹= 1,4-phenylene group, q = 1, X = oxygen atom, n = 0
Embedded image
Compound (h) is obtained by reacting compound (f) with compound (g) in the presence of potassium carbonate. The obtained compound (h) is brominated in the same manner as 1 to obtain the compound (3- (3)).
[0034]
4). A¹, A²= Trans-1,4-cyclohexylene group, n = 2, 3, 4
Embedded image
Compound (i) is acidic with sulfuric acid and one hydroxyl group is brominated to obtain compound (j).
Next, the other hydroxyl group is protected with a tetrahydropyranyl group in the same manner as 1 to obtain the compound (k). Compound (k) is reacted with metallic magnesium to prepare a Grignard reagent, and 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 the compound (3- (4)).
[0035]
5. A²= 1,4-phenylene group, n = 2, 3, 4
Embedded image
One hydroxyl group of compound (o) is protected (p), and the other hydroxyl group is esterified to obtain compound (q). This is reacted with the Grignard reagent (r) to obtain the compound (s). Hereinafter, the compound (3- (5)) is obtained in the same manner as in 1.
[0036]
6). When 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). Subsequently, a compound (y) is obtained by a Wittig reaction, and a compound (3- (6)) is obtained in the same manner as in 1.
[0037]
7). A²= 1,4-phenylene group, q = 0, X = oxygen atom, n = 0
Embedded image
In the same manner as in 3, the compound (3- (7)) can be obtained.
[0038]
8). When X = oxygen atom and 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 ′). Thereafter, the compound (3- (8)) is obtained in the same manner as in 1.
[0039]
9. A¹= Trans-1,4-cyclohexylene group, X = oxygen atom, n = 0, q = 1
Embedded image
The compound (3- (9)) 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.
[0040]
The compound (1) thus obtained has a very large positive dielectric anisotropy (Δε), is excellent in compatibility with other liquid crystal compounds or non-liquid crystal compounds, and chemically. It is a stable compound and is suitable as a liquid crystal composition for lowering the driving voltage of a liquid crystal electro-optical element.
In addition, the compound (1) has a bend elastic constant (K₃₃) And spray elastic constant (K₁₁) And the ratio (K₃₃/ K₁₁In particular, when used in a super twist nematic (STN) type liquid crystal electro-optical element having a high twist angle, the voltage-transmittance characteristic becomes steep and a liquid crystal electro-optical element having excellent display quality can be obtained.
[0041]
Compound (1) is used as a liquid crystal composition by mixing with other liquid crystal compounds or non-liquid crystal compounds (collectively referred to as “other compounds”). The amount of the compound (1) in the liquid crystal composition can be appropriately changed depending on the use, purpose of use, the type of other compounds, etc., but the compound (1) is 0.5 to 50% by mass with respect to the total amount of the liquid crystal composition. Is preferable, and 2 to 20% by mass is particularly preferable. Moreover, two or more types of compounds (1) can be contained in the liquid crystal composition depending on the application, purpose of use, and the like. In that case, the total amount of the compound (1) is preferably 0.5 to 60% by mass, particularly preferably 2 to 30% by mass with respect to the total amount of the liquid crystal composition.
[0042]
Other compounds used in combination with compound (1) include components that improve dielectric anisotropy, components that exhibit liquid crystallinity at high temperatures, other low-viscosity components, components that adjust the refractive index anisotropy value, and cholesteric A component that imparts sexual properties, a component that exhibits dichroism, a component that imparts electrical conductivity, and other various additives. These are appropriately selected depending on the application, required performance and the like, but usually those composed of a liquid crystal compound, a main component having a similar structure to the liquid crystal compound, and an additive component added if necessary.
[0043]
In the liquid crystal composition containing the compound (1), examples of other compounds to be included in the liquid crystal composition include the following. R in the following formula¹And R²Represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a halogen atom, a cyano group or the like. R¹And R²May be the same or different.
R¹-Cy-Cy-R²
R¹-Cy-Ph-R²
R¹-Cy-Ph^FFCN
R¹-Ph-Ph-R²
R¹-Ph-C≡C-Ph-R²
R¹-Cy-COO-Ph-R²
R¹-Cy-COO-Ph^FFCN
R¹-Ph-COO-Ph-R²
R¹-Ph-COO-Ph^FFCN
R¹-Cy-CH = CH-Ph-R²
R¹-Ph-CH = CH-Ph-R²
R¹-Ph-CF = CF-Ph-R²
R¹-Cy-CF = CF-Ph-R²
R¹-Cy-CF = CF-Cy-R²
R¹-Cy-Ph-CF = CF-Ph-R²
R¹-Cy-Ph-CF = CF-Cy-R²
R¹-Ph-Cy-CF = CF-Cy-R²
R¹-Cy-Cy-CF = CF-Ph-R²
R¹-Ph-Ph-CF = CF-Ph-R²
R¹-Cy-CH₂CH₂-Ph-R²
R¹-Cy-Ph-CH₂CH₂-Ph-R²
R¹-Cy-Ph-CH₂CH₂-Cy-R²
R¹-Cy-Cy-CH₂CH₂-Ph-R²
R¹-Ph-CH₂CH₂-Ph-R²
R¹-Ph-Ph-CH₂CH₂-Ph-R²
R¹-Ph-Ph-CH₂CH₂-Cy-R²
R¹-Cy-Ph-Ph-R²
R¹-Cy-Ph-Ph^FFCN
R¹-Cy-Ph-C≡C-Ph-R²
R¹-Cy-Ph-C≡C-Ph^FFCN
R¹-Cy-Ph-C≡C-Ph-Cy-R²
R¹-Cy-CH₂CH₂-Ph-C≡C-Ph-R²
R¹-Cy-CH₂CH₂-Ph-C≡C-Ph-Cy-R²
R¹-Cy-Ph-Ph-Cy-R²
R¹-Ph-Ph-Ph-R²
R¹-Ph-Ph-C≡C-Ph-R²
R¹-Ph-CH₂CH₂-Ph-C≡C-Ph-R²
R¹-Ph-CH₂CH₂-Ph-C≡C-Ph-Cy-R²
R¹-Cy-COO-Ph-Ph-R²
R¹-Cy-COO-Ph-Ph^FFCN
R¹-Cy- Ph- COO- Ph- R²
R¹-Cy-Ph-COO-Ph^FFCN
R¹-Cy-COO-Ph-COO-Ph-R²
R¹-Cy-COO-Ph-COO-Ph^FFCN
R¹-Ph-COO-Ph-COO-Ph-R²
R¹-Ph-COO-Ph-OCO-Ph-R²
These compounds are merely examples, and a hydrogen atom present in a ring structure or a terminal group in the compound may be substituted with a halogen atom, a cyano group, a methyl group, or the like. In addition, the cyclohexane ring or the benzene ring may be substituted with another 6-membered ring or 5-membered ring such as a pyrimidine ring or a dioxane ring, and the linking group between the rings is another divalent bond. Groups such as -CH₂O-, -CH = CH-, -N = N-, -CH = N-, -COOCH₂-, -OCOCH₂-, -COCH₂These may be changed to-etc., and various compounds may be selectively used 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) can be mixed with other compounds in the same manner as the compound (1) and sandwiched between substrates with electrodes as a liquid crystal composition and used as a liquid crystal electro-optical element.
[0044]
The liquid crystal composition of the present invention is sandwiched between substrates with electrodes, such as by being injected into a liquid crystal cell, and twisted nematic method, guest / host method, dynamic scattering method, phase change method, DAP method, dual frequency drive It can be used in various modes such as a method and a ferroelectric liquid crystal display method.
A typical liquid crystal electro-optical element includes a twisted nematic (TN) type liquid crystal electro-optical element. The liquid crystal electro-optical element is expressed here because it is clarified that the liquid crystal electro-optical element can be used for applications other than display applications such as a light control window, an optical shutter, a polarization conversion element, and a variable focus lens. is there.
[0045]
The liquid crystal electro-optical element can be obtained by the following method. First, on a substrate of plastic, glass, etc., if necessary, SiO₂, Al₂O_ThreeUndercoat layer and color filter layer such as₂O_Three-SnO₂(ITO), SnO₂Etc., and after patterning, polyimide, polyamide, SiO as required₂, Al₂O_ThreeAn overcoat layer such as is formed and subjected to orientation treatment. A sealing material is printed on this, it arrange | positions so that an electrode surface may mutually oppose, a periphery is sealed, a sealing material is hardened, and an empty cell is formed.
Further, a liquid crystal composition containing the compound (1) of the present invention is injected into this empty cell, and the injection port is sealed with a sealant to constitute a liquid crystal cell. If necessary, this liquid crystal cell is laminated with polarizing plates, color polarizing plates, light sources, color filters, transflective plates, reflectors, light guide plates, UV-cut filters, etc., printing characters, graphics, etc., non-glare processing, etc. The liquid crystal electro-optic element
[0046]
Note that the above description describes the basic configuration and manufacturing method of the liquid crystal electro-optical element, and other configurations can be employed. For example, a substrate using a two-layer electrode, a two-layer liquid crystal cell having a two-layer liquid crystal layer, a substrate using a reflective electrode, an active matrix device using an active matrix substrate having an active element such as a TFT or MIM, etc. Various configurations can be used.
Furthermore, modes other than the above-described TN type, that is, a super twist nematic (STN) type liquid crystal electro-optical element having a high twist angle, a guest-host (GH) type liquid crystal electro-optical element using a polychromatic dye, a lateral direction In-plane switching (IPS) type liquid crystal electro-optical element that drives liquid crystal molecules parallel to the substrate with an electric field of VA, VA type liquid crystal electro-optical element that aligns liquid crystal molecules vertically with respect to the substrate, and ferroelectric liquid crystal electro-optical element Etc., and can be used in various ways. Further, it can be used not only in a method of electrically writing but also in a method of writing by heat.
[0047]
As described above, the liquid crystal electro-optical element using the liquid crystal composition containing the compound (1) of the present invention can reduce power consumption because of low driving voltage. 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 having excellent display quality can be obtained.
Furthermore, since the liquid crystal composition of the present invention has good compatibility and is chemically stable, a liquid crystal electro-optical element having a wide operating temperature range and storage temperature range and high reliability can be obtained.
[0048]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[Example 1]
360.5 g (2.50 mol) of 1,4-cyclohexanedimethanol was added to 1750 cm of 47% hydrobromic acid.^ThreeAfter adding 245.2 g (2.50 mol) of concentrated sulfuric acid, the mixture was stirred at 80 ° C. for 18 hours.
Next, this reaction solution is neutralized with 25% aqueous sodium hydroxide solution, extracted with MTBE, washed with water, dried, evaporated, purified by distillation under reduced pressure and silica gel column chromatography using 1,2-dichloroethane as a developing solvent. To obtain 137.3 g (yield 27%) of 1-hydroxymethyl-4- (bromomethyl) cyclohexane.
The obtained 1-hydroxymethyl-4- (bromomethyl) cyclohexane (137.3 g, 0.663 mol) was added to hexane (275 cm).^ThreeThen, after adding 6.9 g of Amberlyst 15 (Rohm and Haas ion exchange resin), 66.9 g (0.796 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 4 hours, Amberlyst 15 was removed by filtration, the solvent was distilled off, and silica gel column chromatography using a hexane-toluene mixed solvent was performed to obtain 167.2 g (yield 87%) of the following compound. .
[0049]
Embedded image
167.2 g (0.574 mol) of this compound was added to 502 cm of THF.^ThreeWhat was dissolved in^ThreeAnd it was dripped in the mixture of metal magnesium 15.3g (0.632 mol), stirring. After stirring at room temperature for 2 hours, the reaction solution was cooled to 0 ° C., 65.5 g (0.574 mol) of crotyl acetate, 1.04 g (5.74 mmol) of copper acetate, and 852 cm of THF.^ThreeWas added dropwise. After warming up to room temperature, saturated ammonium chloride aqueous solution 500cm^ThreeThe mixture was stirred for 10 minutes, and the crystals were filtered, extracted with MTBE, washed with water and dried, and then the solvent was distilled off to obtain 147.0 g (yield 96%) of the following compound.
[0050]
Embedded image
147.0 g of this compound was added to 1030 cm of methanol.^Three7.4 g of Amberlyst 15 was added and refluxed for 3 hours. After cooling to room temperature, Amberlyst 15 was removed by filtration, and after distilling off the solvent, vacuum distillation was performed to obtain 51.2 g (yield 51%) of 1-hydroxymethyl-4- (3-pentenyl) cyclohexane described below. . Boiling point 112-114 ° C / 3mmHg
[0051]
Embedded image
86.5 g (0.330 mol) of triphenylphosphine was added to 300 cm of acetonitrile.^ThreeInto the solution, 50.0 g (0.313 mol) of bromine was added dropwise at room temperature and stirred for 30 minutes. To this reaction solution, 50.1 g (0.275 mol) of 1-hydroxymethyl-4- (3-pentenyl) cyclohexane obtained above was added dropwise and stirred at room temperature for 1 hour. 300cm of water^ThreeAfter the addition, the mixture was extracted with hexane, washed with water and dried to distill off the solvent, followed by silica gel column chromatography using hexane as a developing solvent, and 50.6 g of 1-bromomethyl-4- (3-pentenyl) cyclohexane described below. (Yield 75%) was obtained.
[0052]
Embedded image
50.6 g (0.206 mol) of this compound was added to 200 cm of THF.^ThreeWhat was dissolved in^ThreeAfter adding dropwise to a mixture of 5.5 g (0.227 mol) of metallic magnesium and a small amount of iodine while stirring at 40 ° C. while confirming exotherm, the mixture was stirred at the same temperature for 2 hours to prepare a Grignard solution. .
[0053]
38.4 g (0.185 mol) of 3,5-difluorobenzyl bromide was added to 190 cm of toluene.^ThreeA solution prepared by adding 3.5 g (0.0185 mol) of copper iodide was cooled to −30 ° C., and then 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 ammonium chloride solution was added, and the mixture was stirred for 1 hour. The crystals are filtered, extracted with toluene, washed with water and dried, and then the solvent is distilled off, followed by silica gel column chromatography using hexane as a developing solvent and the following 2,6-difluoro-4- [2- [4 -(3-Pentenyl) cyclohexyl] ethyl] benzene (39.2 g, yield 65%) was obtained.
[0054]
Embedded image
39.2 g (0.134 mol) of this compound was added to 200 cm of THF.^ThreeAfter cooling to −60 ° C., butyllithium hexane solution (1.6 mol / dm^Three92cm^ThreeWas dripped. 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 warming to room temperature, dilute hydrochloric acid 500cm^ThreeThe mixture was stirred for 1 hour, extracted with toluene, washed with water and dried, then the solvent was distilled off, and the resulting residue was recrystallized three times with a hexane-toluene mixed solvent to give 2,6-difluoro-4. -21.2 g (47% yield) of [2- [trans-4- (3-pentenyl) cyclohexyl] ethyl] benzoic acid were obtained.
[0055]
Embedded image
21.2 g (0.0630 mol) of this compound was added to 85 cm of tetrachloroethylene.^Three22.5 g (0.189 mol) thionyl chloride and 0.5 cm N, N-dimethylaniline^ThreeAfter stirring overnight at room temperature, the solvent and excess thionyl chloride were distilled off, and the residue was dissolved in 90 cm of toluene.^ThreeDissolved in. 70 cm of toluene cooled to 10 ° C.^ThreeAnd concentrated ammonia water 18cm^ThreeThe mixture was added dropwise to the mixture and stirred at the same temperature for 1 hour. The precipitated white crystals were filtered and dried to obtain 20.1 g (yield 95%) of the following 2,6-difluoro-4- [2- [trans-4- (3-pentenyl) cyclohexyl] ethyl] benzamide. .
[0056]
Embedded image
20.1 g (0.0600 mol) of this compound was added to 100 cm of toluene.^ThreeThen, 17.2 g (0.09 mol) of p-toluenesulfonic acid chloride and 14.2 g (0.18 mol) of pyridine were added and refluxed for 17 hours. After cooling to room temperature, water 200cm^ThreeAnd extracted with toluene, washed with water, washed with alkali, washed and dried, distilled off the solvent, and subjected to alumina column chromatography using hexane as a developing solvent, followed by recrystallization four times with methanol. Of 6.8 g of 2,6-difluoro-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] benzonitrile (36% yield). Melting point 55.3 ° C
[0057]
Embedded image
¹H-NMR (CDCl_ThreeSolvent, TMS standard) spectrum assignments are as follows.
δ (ppm): 0.79-1.98 (multiplet, aliphatic, 19H), 2.67 (triplet, benzyl, 2H), 5.34-5.48 (multiplet, -CH = CH-, 2H), 6.86 (doublet, aromatic, 2H)
¹⁹F-NMR (CHCl_Three, CFCl_ThreeCriteria) The attribution of the spectrum is as follows.
δ (ppm): -105.29 (doublet, J_FH= 9.7Hz)
[0058]
Similarly, the following compounds can be obtained by using 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-difur Rho-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) propiyl]. ) 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.
[0059]
Similarly, the following compounds can be obtained by using corresponding dimethanol instead 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.
[0060]
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- [ -[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- [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] benzo Nitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4- ( -(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.
[0061]
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] benzo Nitrile, 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) cyclohexylmethyl] Oxy] 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-B Nyloxy) 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) bu Til) cyclohexylmethyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (4- (allyloxy) butyl) cyclohexylmethyloxy] cyclohexyl] ethyl] Benzonitrile.
[0062]
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] benzo Nitrile, 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) cyclohexyloxy] Methyl] 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-B Nyloxy) 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) bu Til) cyclohexyloxymethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [trans-4- (4- (allyloxy) butyl) cyclohexyloxymethyl] cyclohexyl] ethyl] Benzonitrile.
[0063]
2,6-difluoro-4- [2- [trans-4- [trans-4- (3-butenyl) cyclohexyloxy] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans- 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.
[0064]
Similarly, the following compound can be obtained by using a corresponding methyl bromide derivative instead of 1-bromomethyl-4- (3-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, 2,6-difluoro-4- [2- [ Trans-4- (trans-1-hexenyl) cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2 [Trans-4- (heptenyl trans-1) cyclohexyl] ethyl] benzonitrile.
[0065]
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.
[0066]
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.
[0067]
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] benzo Nitrile, 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] Rohexyl] 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.
[0068]
2,6-difluoro-4- [2- [trans-4- [2- [trans-4-vinylcyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans- 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- [2- [trans-4- (trans-1-butenyl) cyclohexyl] ethyl] cyclohexyl ] Ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans-4- [2- [trans-4- (to 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 .
[0069]
2,6-difluoro-4- [2- [trans-4- [2- [trans-4-vinyloxycyclohexyl] ethyl] cyclohexyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [trans -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- [to 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.
[0070]
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-a) Ruphenyl) 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.
[0071]
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- ( Lance-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.
[0072]
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, , 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.
[0073]
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, -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.
[0074]
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-diflur B-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.
[0075]
2,6-difluoro-4- [2- (2,6-difluoro-4-vinylphenyl) ethyl] benzonitrile, 2,6-difluoro-4- [2- (2,6-difluoro-4-vinyloxy) Phenyl) 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] benzo Nitrile, 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) pheny ] Ethyl] benzonitrile, 2,6-difluoro-4- [2- [2-fluoro-4- (3-butenyloxy) phenyl] ethyl] benzonitrile.
[0076]
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.
[0077]
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 ] Fe Le] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2- [4- (3-butenyloxy) phenyl] ethyl] phenyl] ethyl] benzonitrile.
[0078]
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-vinyloxy) Phenyl) ethyl] phenyl] ethyl] benzonitrile, 2,6-difluoro-4- [2- [2,6-difluoro-4- [2- (2,6-difluoro-4-allylphenyl) ethyl] Enyl] 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.
[0079]
Similarly, the following compounds 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.
[0080]
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) cyclohexane Sil] 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.
[0081]
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-penteni Oxy) 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) cyclo Cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile.
[0082]
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] cyclo Xyl] 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-penteni Oxy) cyclohexyl] phenyl] ethyl] cyclohexyl] benzonitrile.
[0083]
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- ( Lance-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.
[0084]
[Example 2]
The clearing point (nematic-isotropic phase transition point, NI) of the liquid crystal composition “ZLI-1565” manufactured by Merck was 85.9 ° C. A silicon oxide coat layer was formed on a substrate with an ITO electrode, and this liquid crystal composition was sandwiched between the rubbed substrates to prepare a TN liquid crystal cell with a substrate spacing of 8.0 μm. When the threshold voltage of this liquid crystal cell at 25 ° C. was measured, it was 2.41V.
[0085]
[Example 3]
[2,6-Difluoro-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] benzonitrile synthesized in Example 1 was added to 80 wt% of a liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc. 20 wt% was added. The clearing point (N-I) of this liquid crystal composition was 62.8 ° C. Using this liquid crystal composition, a TN liquid crystal cell was prepared in the same manner as in Example 2. The threshold voltage of the liquid crystal cell at 25 ° C. of this liquid crystal cell was 1.44 V, and the driving voltage was greatly reduced as compared with the liquid crystal cell of Example 2.
[0086]
[Example 4]
The clearing point (N-I) of the liquid crystal composition “ZLI-2293” manufactured by Merck was 84.4 ° C. A silicon oxide coat layer was formed on a substrate with an ITO electrode, and this liquid crystal composition was sandwiched between rubbed substrates to produce STN type liquid crystal cells with a substrate spacing of 6.5 μm. When the threshold voltage of this liquid crystal cell at 25 ° C. was measured, it was 2.16V. The voltage V at which the transmittance in the normal direction changes by 10%_TenAnd the voltage V changing 90%₉₀Γs (= V_Ten/ V₉₀) Was 0.912.
[0087]
[Example 5]
[2,6-Difluoro-4- [2- [trans-4- (trans-3-pentenyl) cyclohexyl] ethyl] benzonitrile synthesized in Example 1 was added to 80 wt% of a liquid crystal composition “ZLI-2293” manufactured by Merck & Co., Inc. 20 wt% was added. The clearing point (N-I) 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 driving voltage was significantly lower than that of the liquid crystal cell of Example 4. Further, γs was 0.920, and the voltage-transmittance characteristics were steeper than the liquid crystal cell of Example 4.
[0088]
【The invention's effect】
As described above, the compound (1) of the present invention has a very large positive dielectric anisotropy, and a liquid crystal optical element using a liquid crystal composition containing the compound (1) can be driven at a low voltage, and Excellent display quality. Further, since the compatibility in the liquid crystal composition is good and chemically stable, a liquid crystal electro-optical element having a wide use temperature range and a wide storage temperature range and high reliability can be obtained. The 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.

Claims (3)

A difluorobenzene compound represented by the formula (2).
However, symbols R, X, A ¹ , A ² , A ³ , Y, m, n, q and r in formula (2) have the following meanings (where A ² is unsubstituted 1,4- When it is a phenylene group, q is 1, Y is a single bond, and r is 0, A ¹ is not an unsubstituted 1,4-phenylene group).
R: a linear alkyl group having 1 to 5 carbon atoms or a hydrogen atom.
-CH = CH-: trans-vinylene group.
X: an oxygen atom or a single bond.
A ¹ , A ² : each independently 1,4-phenylene group or trans-1,4-cyclohexylene group. The groups A ¹ and A ² may be unsubstituted or each may have one or more fluorine atoms as a substituent.
A ³ : 1,4-phenylene group or trans-1,4-cyclohexylene group. If A ³ is trans-1,4-cyclohexylene group, this group is unsubstituted. When A ³ is a 1,4-phenylene group, this group has one or more fluorine atoms as a substituent.
_{Y: -CH 2 CH 2 -,} - CH 2 O -, - OCH 2 -, - O- 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. The compound represented by formula (3) is reacted with metallic magnesium to form a Grignard reagent, and then reacted with the compound represented by formula (4) in the presence of a transition metal catalyst. 2. A process for producing a difluorobenzene compound according to 1 .
However, the symbols R, X, A ¹ , A ² , A ³ , Y, m, n, q and r in formulas (3) and (4) have the same meaning as in formula ( 2 ), and B ¹ , B ² has the following meaning.
B ¹ : Chlorine atom, bromine atom or iodine atom.
B ² : a leaving group. A compound represented by formula (3) is reacted with metallic magnesium to form a Grignard reagent, and then reacted with a compound represented by formula (4) in the presence of a transition metal catalyst, which is represented by formula (2). A method for producing a difluorobenzonitrile compound represented by the following formula (1), wherein the method comprises a step of synthesizing a compound.
However, the symbols R, X, A ¹ , A ² , A ³ , Y, m, n, q and r in formula (1) have the same meaning as in formula (2) (provided that A ² is non- When it is a substituted 1,4-phenylene group, q is 1, Y is a single bond, and r is 0, A ¹ is not an unsubstituted 1,4-phenylene group.