JP3535545B2 - Difluoroethylene derivative compound, liquid crystal composition containing the same, and liquid crystal electro-optical element - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a difluoroethylene derivative compound , a liquid crystal composition containing the same and a liquid crystal electric compound.
Regarding optical elements .

[0002]

2. Description of the Related Art Liquid crystal display devices include clocks, calculators,
In recent years, measuring instruments, automobile instruments, copying machines, cameras, OA
It has begun to be used in various applications such as device display devices and home appliance display devices, and various performance requirements such as wide operating temperature range, low operating voltage, high-speed response, high contrast ratio, wide viewing angle, chemical stability, etc. Has been done.

However, at present, no compound satisfying all of these properties alone, a state that meets the required performance as a liquid crystal composition by mixing a plurality of liquid crystal compounds, and non-liquid crystal compounds. Therefore, it is desired to develop a liquid crystal compound or a non-liquid crystal compound which is excellent in one or more characteristics, not in all of the various characteristics.

[0004]

In liquid Akirahyo示素Ko FIELD [0005], low-voltage drive, high definition display, a high contrast ratio,
Wide viewing angle characteristic, a low temperature response characteristic, performance improvement, such as wide operating temperature range
The above is desired and there is a tendency for improving one of them to sacrifice the other.

In particular, recently, low-voltage driving and high speed response in battery-driven, high-definition displays and high-speed response in OA equipment or the like, so that high-speed response or in a wide operating temperature range low response in automobile display, etc. In addition, improvement of the response speed is desired.

There are several possible methods for improving the response speed , and one of them is the use of a low-viscosity liquid crystal composition. That is, if the viscosity of the liquid crystal composition is reduced, the response speed is improved, and it is possible to display at a practical speed even at low temperatures. Also, if the response speed is the same as before,
It is possible to drive at a lower voltage or drive with a higher duty ratio , that is, high-definition drive is possible.

For such a purpose, JP-A-3-410 is used.
37 or p as shown in JP-A-3-294386, p'- disubstituted difluorostilbene compound has been proposed. This compound we have a table by Ru chemical structure by the following formula (3).

[0008]

[Chemical 1]

However , R ^A and R ^B in the formula (3) mean an n-alkyl group, an n-alkoxy group and an n-alkoxycarbonyl group.

[0010] compound represented by formula (3) is Ah at low viscosity
Ri, that have improved stability to light than the stilbene compound which is not fluorinated. However, the stability against light is still inferior to the commonly used general liquid crystal compounds, and the use environment is limited, and it is often necessary to use an ultraviolet cut filter together.
Therefore, it is a liquid crystal compound with low viscosity and high stability to light.
Things were wanted.

[0011]

The present invention solves the above problems.
New to decideCompoundIs providedThe following formula
Providing a difluoroethylene derivative compound represented by (1)
CompanionDo.

R ^1- (A ¹ ) _m -Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1)

However , in the formula (1), A ¹ , A ² , A ³ ,
A ⁴ , Y ¹ , Y ² , R ¹ , R ² , m and n are as follows.

A ³ is a trans-1,4-cyclohexylene group, and A ¹ , A ² and A ⁴ are independently of each other a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or 1,4-cyclohexenylene group, or whether these cyclic groups are each unsubstituted have one or more halogen atoms or a cyano group as a substituent, constituting a ring in these ring groups One or more = CH- groups may be substituted with a nitrogen atom, and one or more -C forming a ring.
H ₂ - group oxygen atom or may be substituted by a sulfur atom.

Y ¹ and Y ² are independently of each other --COO--,-
OCO -, - C≡C -, - CH 2 CH 2 -, - CH = CH
-, - OCH ₂ -, - shows a CH ₂ O- or a single bond.

R ¹ and R ² independently of each other have 1 to 10 carbon atoms.
Alkyl group, or a halogen atom a cyano group, in the case of the alkyl group, the carbon in the alkyl group - oxygen atom between carbon bonded - carbon between also between carbon bond between this alkyl group and cyclic group may also carbonyloxy group optionally inserted oxycarbonyl group, a carbon in the alkyl group of this - a part of carbon bonds is a triple bond or may be a double bond, the alkyl group of this of one -CH ₂ - group may be substituted by a carbonyl group, or a part of hydrogen atoms in the alkyl group of this may be the whole is replaced with a fluorine atom, yet, R ^1, at least one of R ² is, or carbon is a chlorine atom - partially triple bond Moshiku carbon bonds is a group having a double bond.

M and n each independently represent 0 or 1.

The present invention also provides the following formula ( 4 ) (provided that A ² , A ³ , R ¹ and R ^{2 in} the formula ( 4 ) are represented by the formula (1)
Shows the same as . ) Provides difluoro derivative compound represented by the.

R ¹ -A ² -CF = CF-A ³ -R ² ( 4 )

Further, the present invention is,formula(1) AlsoIs an expression
(Four) CompoundAt least oneA liquid crystal composition containing
Moreover,TheLiquid crystal composition sandwiched between substrates with electrodes
Provide liquid crystal electro-optical elementDo.

The compound of the formula (1) of the present invention has a relatively large refractive index anisotropy (Δn), has a low viscosity,
In addition, it is a compound that has excellent compatibility with other liquid crystal compounds or non-liquid crystal compounds and is chemically stable.

Further, the compound of the formula (1) of the present invention is stable to light and has improved elasticity (K ₃₃ / K ₁₁ ) as compared with the compound of the above-mentioned formula (3). ) is high contrast of increased liquid crystal upper limit temperature, ie N-I point (T
_C) is a liquid crystal temperature range is increased to rise, such as the viscosity (eta) is advantageously reduced speed response, a compound <br/> each characteristic is improved.

Especially high speed super twist nematic ( S
As a compound for a TN ) type liquid crystal electro-optical element , it is superior to the compound of the formula (3) and useful.

[0024] In the compounds of the present invention, there is the following compounds. The following compounds are examples of compounds having two rings .

R ¹ -A ² -CF = CF-A ³ -R ² (4)

More specifically, the compound of the formula (4) includes the following compounds. In the following description, not only the compound of formula (4) but also "-Ph-" represents a 1,4-phenylene group and "-Cy-" represents a trans-1,4-cyclohexylene group. , "- Ch-" represents a 1,4-cyclohexylene group, "- PhF -"
Also mono-fluoro-1,4-phenylene group represents a polyfluoro-1,4-phenylene group.

R ¹ -Ph-CF = CF-Cy-R ² (4A) R ¹ -Cy-CF = CF-Cy-R ² (4B) R ¹ -Ch-CF = CF-Cy-R ² (4C ) R ¹ -PhF-CF = CF-Cy-R ² (4D)

The following compounds are examples of compounds having three rings.

R ¹ -A ¹ -A ² -CF = CF-A ³ -R ² (51) R ¹ -A ² -CF = CF-A ³ -A ⁴ -R ² (52)

More specifically, the compound of formula (51) or formula (52) includes the following compounds.

R ¹ -Ph-Cy-CF = CF-Ph-R ² (5A) R ¹ -Ph-Cy-CF = CF-Cy-R ² (5B) R ¹ -Ph-Cy-CF = CF- Ch-R ² (5C) R ¹ -Cy-Cy-CF = CF-Ph-R ² (5D) R ¹ -Cy-Cy-CF = CF-Cy-R ² (5E) R ¹ -Cy-Cy- CF = CF-Ch-R ² (5F) R ¹ -Ch-Cy-CF = CF-Ph-R ² (5G) R ¹ -Ch-Cy-CF = CF-Cy-R ² (5H) R ^1- Ch-Cy-CF = CF-Ch-R ² (5I) R ¹ -PhF-Cy-CF = CF-Ph-R ² (5J) R ¹ -PhF-Cy-CF = CF-Cy-R ² (5K ) R ¹ -PhF-Cy-CF = CF-Ch-R ² (5L) R ¹ -Ph-Cy-CF = CF-PhF-R ² (5M) R ¹ -Cy-Cy-CF = CF-PhF- R ² (5N) R ¹ -Ch-Cy-CF = CF-PhF-R ² (5O) R ¹ -Cy-CF = CF-Ph-Ph-R ² (5P) R ¹ -Cy-CF = CF- Ph-Cy-R ² (5Q) R ¹ -Cy-CF = CF-Ph-Ch-R ² (5R) R ¹ -Cy-CF = CF-Ch-Ph-R ² (5S) R ¹ -Cy- CF = CF-Ch-Cy-R ² (5T) R ¹ -Cy-CF = CF-Ch-Ch-R ² (5U) R ¹ -Cy-CF = CF-PhF-Ph-R ² (5V) R ¹ -Cy-CF = CF-PhF-Cy-R ² (5W) R ¹ -Cy-CF = CF-PhF-Ch-R ² (5X)

Further, as a compound having four rings, there are the following compounds.

R ¹ -A ¹ -A ² -CF = CF-A ³ -A ⁴ -R ² (6)

More specifically, the compound of the formula (6) includes the following compounds.

R ¹ -Ph-Cy-CF = CF-Ph-Ph-R ² (6A) R ¹ -Ph-Cy-CF = CF-Cy-Cy-R ² (6B) R ¹ -Ph-Cy- CF = CF-Ch-Ch-R ² (6C) R ¹ -Ph-Cy-CF = CF-Ph-Cy-R ² (6D) R ¹ -Ph-Cy-CF = CF-Ph-Ch-R ² (6E) R ¹ -Ph-Cy-CF = CF-Cy-Ph-R ² (6F) R ¹ -Ph-Cy-CF = CF-Cy-Ch-R ² (6G) R ¹ -Ph-Cy- CF = CF-Ch-Ph-R ² (6H) R ¹ -Ph-Cy-CF = CF-Ch-Cy-R ² (6I) R ¹ -Cy-Cy-CF = CF-Ph-Ph-R ² (6J) R ¹ -Cy-Cy-CF = CF-Cy-Cy-R ² (6K) R ¹ -Cy-Cy-CF = CF-Ch-Ch-R ² (6L) R ¹ -Cy-Cy- CF = CF-Ph-Cy-R ² (6M) R ¹ -Cy-Cy-CF = CF-Ph-Ch-R ² (6N) R ¹ -Cy-Cy-CF = CF-Cy-Ch-R ² (6O) R ¹ -Cy-Cy-CF = CF-Ch-Ph-R ² (6P) R ¹ -Cy-Cy-CF = CF-Ch-Cy-R ² (6Q) R ¹ -Ch-Cy- CF = CF-Ph-Ph-R ² (6R)

R ¹ -Ch-Cy-CF = CF-Ch-Ch-R ² (6S) R ¹ -Ch-Cy-CF = CF-Ph-Cy-R ² (6T) R ¹ -Ch-Cy- CF = CF-Ph-Ch-R ² (6U) R ¹ -Ch-Cy-CF = CF-Cy-Ch-R ² (6V) R ¹ -Ch-Cy-CF = CF-Ch-Ph-R ² (6W) R ¹ -Ch-Cy-CF = CF-Ch-Cy-R ² (6X) R ¹ -Ph-Cy-CF = CF-PhF-Ph-R ² (6Y) R ¹ -Ph-Cy- CF = CF-PhF-Cy-R ² (6Z) R ¹ -Ph-Cy-CF = CF-PhF-Ch-R ² (6a) R ¹ -Cy-Cy-CF = CF-PhF-Ph-R ² (6b) R ¹ -Cy-Cy-CF = CF-PhF-Cy-R ² (6c) R ¹ -Cy-Cy-CF = CF-PhF-Ch-R ² (6d) R ¹ -Ch-Cy- CF = CF-PhF-Ph-R ² (6e) R ¹ -Ch-Cy-CF = CF-PhF-Cy-R ² (6f) R ¹ -Ch-Cy-CF = CF-PhF-Ch-R ² (6g)

In addition, in the case of a compound having three or more rings, there are the following compounds in which Y ¹ and Y ² between the rings are changed to other than a single bond.

R ¹ -Ph-C ≡ C-Ph-CF = CF-Cy-R ² (7A) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF = CF-Cy-R ² (7B) R ¹ -Ph-OCH ₂ -Ph-CF = CF-Cy-R ² (7C) R ¹ -Ph-CH ₂ O-Ph-CF = CF-Cy-R ² (7D) R ¹ -Ph-COO-Ph- CF = CF-Cy-R ² (7E) R ¹ -Ph-OCO-Ph-CF = CF-Cy-R ² (7F) R ¹ -Ph-C ≡ C-Cy-CF = CF-Ph-R ² (7G) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ph-R ² (7H) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Ph-R ² (7I) R ^1- Ph-CH ₂ O-Cy-CF = CF-Ph-R ² (7J) R ¹ -Ph-COO-Cy-CF = CF-Ph-R ² (7K) R ¹ -Ph-OCO-Cy-CF = CF-Ph-R ² (7L) R ¹ -Ph-C ≡ C-Cy-CF = CF-Cy-R ² (7M) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Cy-R ² (7N) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Cy-R ² (7O) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Cy-R ² (7P) R ^1- Ph-COO-Cy-CF = CF-Cy-R ² (7Q) R ¹ -Ph-OCO-Cy-CF = CF-Cy-R ² (7R) R ¹ -Ph-C ≡ C-Cy-CF = CF-Ch-R ² (7S) R ¹ -Ph-CH ₂ CH ₂ -Cy-CF = CF-Ch-R ² (7T) R ¹ -Ph-OCH ₂ -Cy-CF = CF-Ch-R ² (7U) R ¹ -Ph-CH ₂ O-Cy-CF = CF-Ch-R ² (7V) R ¹ -Ph-COO-Cy-CF = CF-Ch-R ² (7W) R ¹ -Ph- OCO-Cy-CF = CF-Ch-R ² (7X)

R ¹ -Ph-C ≡ C-Ph-CF = CF-Cy-Ph-R ² (8A) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF = CF-Cy-Ph-R ² ( 8B) R ¹ -Ph-OCH ₂ -Ph-CF = CF-Cy-Ph-R ² (8C) R ¹ -Ph-CH ₂ O-Ph-CF = CF-Cy-Ph-R ² (8D) R ¹ -Ph-COO-Ph-CF = CF-Cy-Ph-R ² (8E) R ¹ -Ph-OCO-Ph-CF = CF-Cy-Ph-R ² (8F) R ¹ -Ph-C ≡ C-Ph-CF = CF-Cy-Cy-R ² (8G) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF = CF-Cy-Cy-R ² (8H) R ¹ -Ph-OCH _2- Ph-CF = CF-Cy-Cy-R ² (8I) R ¹ -Ph-CH ₂ O-Ph-CF = CF-Cy-Cy-R ² (8J) R ¹ -Ph-COO-Ph-CF = CF-Cy-Cy-R ² (8K) R ¹ -Ph-OCO-Ph-CF = CF-Cy-Cy-R ² (8L) R ¹ -Ph-C ≡ C-Ph-CF = CF-Cy- Ch-R ² (8M) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF = CF-Cy-Ch-R ² (8N) R ¹ -Ph-OCH ₂ -Ph-CF = CF-Cy-Ch- R ² (8O) R ¹ -Ph-CH ₂ O-Ph-CF = CF-Cy-Ch-R ² (8P) R ¹ -Ph-COO-Ph-CF = CF-Cy-Ch-R ² (8Q ) R ¹ -Ph-OCO-Ph-CF = CF-Cy-Ch-R ² (8R)

Further, also a halogen atom part of the hydrogen atoms of the A ³ trans-1,4-cyclohexylene group may be group substituted by a cyano group. Also, A ¹ , A ² , A ⁴
Is a group in which a part of hydrogen atoms of the ring group is substituted with a halogen atom or a cyano group, or a part of = CH- group forming a ring is replaced with a nitrogen atom, or -C forming a ring.
H ₂ - the following compounds some examples obtained by substituting the oxygen atom or sulfur atom of the group.

[0041]

[Chemical 2]

The compounds of formula (1) of the present invention is mixed with at least one other liquid crystal compounds and / or non-liquid crystal compound <br/>, it is used in the liquid crystal composition. Thereby, it is possible to make the liquid crystal composition and low viscosity, the liquid crystal electro
When used as an optical element, high-speed response becomes possible.

Examples of the compound to be mixed with the compound of the present invention are as follows. In addition, R ^C and R ^D in the following formulas represent groups such as an alkyl group, an alkoxy group, a halogen atom and a cyano group. Moreover, "-NON-" represents an azoxy group.

R ^C -Cy-Cy-R ^D R ^C -Cy-Ph-R ^D R ^C -Ph-Ph-R ^D R ^C -Cy-COO-Ph-R ^D R ^C -Ph-COO-Ph- R ^D R ^C -Cy-CH = CH-Ph-R ^D R ^C -Ph-CH = CH-Ph-R ^D R ^C -Cy-CH ₂ CH ₂ -Ph-R ^D R ^C -Ph-CH ₂ CH ₂ -Ph-R ^D R ^C -Ph-N = N-Ph-R ^D R ^C -Ph-NON-Ph-R ^D R ^C -Cy-COS-Ph-R ^D R ^C -Cy-Ph-Ph- R ^D R ^C -Cy-Ph-Ph-Cy-R ^D R ^C -Ph-Ph-Ph-R ^D R ^C -Cy-COO-Ph-Ph-R ^D R ^C -Cy-Ph-COO-Ph- R ^D R ^C -Cy-COO-Ph-COO-Ph-R ^D R ^C -Ph-COO-Ph-COO-Ph-R ^D R ^C -Ph-COO-Ph-OCO-Ph-R ^D

[0045]

[Chemical 3]

[0046] Incidentally, these compounds merely exemplification
Ri, ring structure or end group hydrogen atom a halogen atom, a cyano group, may be substituted with a methyl group, a cyclohexane ring, a benzene ring to another six-membered ring, five-membered ring, for example, pyridine ring, dioxane may be substituted in the ring or the like, can also be further modified the linking group between the ring and the ring, various compounds may be selected using for the desired performance.

The liquid crystal composition of the present invention, by, for example injected into the liquid crystal cell is sandwiched between substrates dated electrodes, a liquid crystal electro-optical element.

As a typical liquid crystal electro-optical element, there is a twist nematic (TN) type liquid crystal electro-optical element. Note that the reason expressed as a liquid crystal electro-optical device, other than the display applications, for example, dimming the window, optical shutter, a order to Ru can be used in the polarization exchange element.

The liquid crystal electro-optical element is used in various modes such as a TN system, a guest-host (GH) system, a dynamic scattering system, a phase change system, a DAP system, a dual frequency drive system and a ferroelectric liquid crystal display system. kill in use.

Specific examples of the structure and manufacturing method of the liquid crystal electro-optical element will be shown below. Table of substrates such as plastic and glass
An undercoat layer or a color filter layer of SiO ₂ , Al ₂ O ₃ or the like is formed on the surface , if necessary . And In
After providing electrodes such as ₂ O ₃ —SnO ₂ (ITO) and SnO ₂ and patterning, an overcoat layer of polyimide, polyamide, SiO ₂ , Al ₂ O ₃ or the like is formed if necessary, and an orientation treatment is performed. A sealing material is printed on this, the electrodes are arranged so as to face each other, the periphery is sealed, and the sealing material is cured to form an empty cell.

The liquid crystal composition of the present invention is injected into this empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, a polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflection plate, a reflection plate, a light guide plate, an ultraviolet ray cut filter, etc. are laminated on this liquid crystal cell, characters, figures, etc. are printed, and non-glare processing is performed. Then, the liquid crystal electro-optical element is obtained.

[0052] Incidentally, the above description is intended showing a basic configuration and manufacturing method of a liquid crystal electro-optical device of the present invention,
In addition , various structures such as a substrate using a two-layer electrode, a two-layer liquid crystal cell having two liquid crystal layers, an active matrix element using an active matrix substrate having active elements such as TFTs and MIMs are available. the recited Ru.

[0053] The liquid crystal composition of the present invention by using a liquid crystal electro-optical device, even when the driving of the high duty ratio,
High-speed response can be expected. Therefore, it is suitable for an STN type liquid crystal electro-optical element having a high twist angle , which has been receiving attention in recent years. In addition, a GH type liquid crystal display device using a polychromatic dye,
It can also be used as a ferroelectric liquid crystal electro-optical element.

The compound of formula (1) of the present invention is produced, for example, according to the following method.

[0055]

[Chemical 4]

The symbols in the formula are as described above.
Has the same meaning as.

[0057]

[0058]

[0059] was reduced by lithium aluminum hydride carboxylic acid derivative of the formula (10) to an alcohol derivative of formula (11). Next, by oxidizing the compound of formula (11) <br/> at pyrid two um chlorochromate, formula (1
The aldehyde derivative of 2) is used.

Then, the obtained compound of formula (12) is reacted with dibromodifluoromethane and trisdimethylaminophosphine to obtain a 1,1-difluoroethylene compound of formula (13). Then, it is fluorinated with cobalt trifluoride to give a 1,1,1,2-tetrafluoroethane compound of formula (14), which is de-HFed with t-butyllithium to give trifluoroethylene of formula (15). It is a compound. Finally by reaction with a lithium compound of formula (16), difluoroethylene of formula (1)
Derivative compounds can be obtained.

Also,formulaR of the compound of (1)¹, R²Reed
Introduce a radicalToIs R¹, R²Is a hydrogen atomFormula
Friedel Cla of compound (1) and acyl halide
The foot reaction may be used. Introduce a cyano groupTo
Is R¹, R²Is a bromine atom or an iodine atomFormula
The compound (1) may be reacted with CuCN. Also,
formulaY of the compound of (1)¹To the vinylLesGroup (-C = C-)
IntroduceToIs R¹, R²Is a chlorine atom or bromine atom
Is an iodine atomFormulaCompound of (1) and alkenyl green
A coupling reaction with a near compound may be used. Well
Was,formulaY of the compound of (1)¹ToChineseGroup (-C≡C
-) Is introducedToIs R¹, R²Is a bromine atom or iodine
Is an atomFormulaCompound of (1) and alkynyl lithium compound
A coupling reaction with a substance may be used.

[0062]

EXAMPLES Examples 1-4, 6 and 9 are carried out below.
Examples, Examples 5, 7 and 8 are comparative examples. [Example 1] <First Step> 1 liter four-necked flask, lithium aluminum
22.3 g (0.588 mol) of hydride and 300 ml of tetrahydrofuran (THF) were added, and the mixture was cooled to 0 ° C. 100 g (0.588 mol) of trans-4-n-propylcyclohexanecarboxylic acid was added to THF.
The solution dissolved in 300 ml was added dropwise with stirring at 10 ° C. or lower over 2 hours. After further stirring at room temperature for 12 hours, 200 ml of 20% sulfuric acid aqueous solution was added, extracted with ether, washed with water, dried, distilled off the solvent, and further distilled under reduced pressure (88 ° C / 4 mmHg) to trans-4-n-.
Propyl cyclohexanemethanol (n-C ₃ H ₇ -Cy
89.3 g (yield 97%) of —CH ₂ OH) was obtained.

[0063] <Second step> Next, the four-neck 2 liter flask, pyridinium chlorochromate and (PCC) 370.2g (1.717
mol) and 23.5 g (0.286 m) of sodium acetate
ol) and methylene chloride 1.2 narrowing specification liters, at room temperature, trans -4-n-propyl cyclohexane methanol 89.3 g (0.57 obtained in the first step
2 mol) of methylene chloride solution was added dropwise. After stirring at room temperature for 1 hour, 1 liter of ether was added, and anhydrous Mg was added.
SO ₄ was added and the tar material was filtered off. The filtrate was concentrated under reduced pressure, 200 ml of ether was added again, and the tar-like substance was filtered off. The filtrate was concentrated under reduced pressure, purified by silica gel column chromatography, and the obtained crude liquid was distilled under reduced pressure (64 ° C./3 mmHg) to give trans-4-n.
- propyl cyclohexane aldehyde (n-C ₃ H ₇ -C
56.0 g (yield 64%) of y-CHO) was obtained.

<Third Step> 400 g of triglyme dehydrated with CaH ₂ was placed in a 1-liter four-necked flask equipped with a cooling tube and a gas blowing tube.
Put ml, cooled to 0 ° C., was bubbled 101g (0.481mol) of dibromodifluoromethane methane. Then 0
156.7% of trisdimethylaminophosphine at
g (0.961mol) and a triglyme of 200ml
The mixed solution of was added dropwise over 15 minutes. 1 at room temperature after dropping
After stirring for 5 minutes, trans-4-n obtained in the second step
-Propylcyclohexanaldehyde 37.0 g (0.
(24 mol) and 100 ml of triglyme are added dropwise at room temperature over 15 minutes, and the mixture is further heated at 85 ° C. for 2 minutes.
Reacted for hours.

After cooling to 0 ° C., 300 ml of water was added, and n-
After extraction with hexane, washing with water and drying, the solvent was distilled off, the obtained crude liquid was purified by silica gel column chromatography, and the obtained crude liquid was distilled under reduced pressure (78 ° C / 20 m).
m (Hg) to give 2- (trans-4-n-propylcyclohexyl) -1,1-difluoroethylene (n-C _{3
H 7 -Cy-CH = CF 2} ) a 28.6 g (63% yield)
Obtained.

<Fourth Step> The 2- (trans-4-n-propylcyclohexyl) obtained in the third step was placed in a 2-liter autoclave.
28.6 g (0.15) of -1,1-difluoroethylene
2 mol) and 123.4 g (1.0
6 mol), 1 ml of water and FC-113 (CCl ₂ F
1000 ml of CClF ₂ ) was charged and reacted at 100 ° C. for 3 hours. After cooling, the inorganic salt is filtered off and the organic phase is washed with 10
% NaHCO ₃ aqueous solution, further washed with water, the solvent was distilled off, and the resulting crude liquid was purified by silica gel column chromatography to give 2- (trans-4-n-propylcyclohexyl) -1,1. , crude liquid of 1,2-tetrafluoroethane _{(n-C 3 H 7 -Cy} -CHFCF 3) 1
5.5 g (86% purity) was obtained.

<Fifth Step> The 2- (trans-4-n-propylcyclohexyl) -obtained in the fourth step was placed in a 1-liter four-necked flask.
Crude liquid of 1,1,1,2-tetrafluoroethane 15.5
g and 200 ml of dry THF were charged, and the mixture was cooled to -78 ° C. Then, 44.2 ml (0.07) of a n-pentane solution of t- butyllithium (1.6 mol / liter) was used.
mol), and was added dropwise over 30 minutes. Furthermore, after reacting at -78 ° C for 2 hours, the temperature was raised to room temperature, and 1N hydrochloric acid was added to
00 ml was added and the organic phase was separated. After the aqueous phase was extracted with n-hexane, the organic phase was combined, washed with water and dried, the solvent was distilled off, and the resulting crude liquid was purified by silica gel column chromatography to give 2- (trans-4-n). - propyl cyclohexyl) -1,1,2-trifluoroethylene _{(n-C 3 H 7 -Cy} -CF = CF 2) a 7.53 g (62% yield).

[0068] The four-neck flask <Sixth Step> 300 ml, 4-chloro iodobenzene 6.02 g (25.2 mmol) and dry ether
30 ml was charged and cooled to -78 ° C. Then n
- butyllithium n- hexane solution (1.63 mol
/ Liter) was added dropwise in an amount of 17 ml (27.8 mmol) over 15 minutes. Furthermore, after stirring at −78 ° C. for 1 hour,
3.8ml of tetramethylenediamine (TMEDA)
(25.5 mmol) was added, and 1.3 g of 2- (trans-4-n-propylcyclohexyl) -1,1,2-trifluoroethylene obtained in the fifth step.
A mixed solution of (6.3 1 mmol) and 60 ml of dry THF was added dropwise over 30 minutes. After further reacting at the same temperature for 2 hours, the temperature was raised to room temperature, 500 ml of 1N hydrochloric acid was added, and the organic phase was separated. After extracting the aqueous phase with n-hexane,
After washing with water and drying together with the organic phase , the solvent was distilled off, the resulting crude liquid was purified by silica gel column chromatography, and the obtained solid was recrystallized from methanol,
The following (E) -1- (4-chlorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-
Difluoroethylene _{(n-C 3 H 7 -Cy} -CF = CF-
0.66 g (yield 35%) of Ph-Cl) was obtained.

[0069]

[Chemical 5]

The analysis results of this compound are shown in Table 1.

The following compounds can be obtained in the same manner as in Example 1.

C H ₃ -Cy-CF = CF-Ph-Cl nC ₅ H ₁₁ -Cy-CF = CF-Ph-Cl CF ₃ -Cy-CF = CF-Ph-Cl F-Cy-CF = CF- Ph-Cl CH ₃ O-Cy-CF = CF-Ph-Cl nC ₃ H ₇ O-Cy-CF = CF-Ph-Cl CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-Cl CH ₃ C≡ C-Cy-CF = CF-Ph-Cl C ₃ H ₇ -Cy-CF = CF-PhF-Cl

[0073][Example2]An example In the sixth step of 1, 4-chloroiodobenze
The6.02gInstead of 1-methyl-2- (4-iodo
6.10 g (25.2 mmo) of phenyl) acetylene
l) Other than usingIs an examplePerform the same reaction as in 1.below
(E) -1- (4- (1-PropiNil) Phenyl) -2
-(Trans-4-n-propylcyclohexyl)-
1,2-difluoroethylene (n-C₃H₇-Cy-CF
= CF-Ph-C≡CCH₃) 0.47 g (yield 25
%)Obtained.

[0074]

[Chemical 6]

The analysis results of this compound are shown in Table 2.

The following compounds can be obtained in the same manner as in Example 2.

C H ₃ -Cy-CF = CF-Ph-C ≡CCH ₃ nC ₅ H ₁₁ -Cy-CF = CF-Ph-C ≡CCH ₃ CF ₃ -Cy-CF = CF-Ph-C ≡CCH ₃ F-Cy-CF = CF-Ph-C ≡CCH ₃ CH ₃ O-Cy-CF = CF-Ph-C ≡CCH ₃ nC ₃ H ₇ O-Cy-CF = CF-Ph-C ≡CCH ₃ CH ₂ = CHCH ₂ -Cy-CF = CF-Ph-C ≡CCH ₃ CH ₃ C ≡C-Cy-CF = CF-Ph-C ≡CCH ₃ C ₃ H ₇ -Cy-CF = CF-PhF-C ≡ CCH ₃ C ₃ H ₇ -Cy-CF = CF-Ph-C≡CH C ₃ H ₇ -Cy-CF = CF-Ph-C≡CF

Example 3 In the sixth step of Example 1, trans-1-methyl-2- was used instead of 6.02 g of 4- chloroiodobenzene.
(4-iodophenyl) ethyl Ren the 6.15 g (25.
2 mmol) except that the conducting reactions as in Example 1, below
Serial of (E) -1- (4- (trans-1-pro propenyl)
Phenyl) -2- (trans -4-n-propyl) -1,2-difluoro-ethylene (n-C ₃ H ₇
-Cy-CF = CF-Ph- CH = CHCH 3) 0.
42 g (yield 22%) was obtained.

[0079]

[Chemical 7]

Table 3 shows the analysis results of this compound.

The following compounds can be obtained in the same manner as in Example 3.

C H ₃ -Cy-CF = CF-Ph-CH = CHCH ₃ nC ₅ H ₁₁ -Cy-CF = CF-Ph-CH = CHCH ₃ CF ₃ -Cy-CF = CF-Ph-CH = CHCH ₃ F-Cy-CF = CF-Ph-CH = CHCH ₃ CH ₃ O-Cy-CF = CF-Ph-CH = CHCH ₃ nC ₃ H ₇ O-Cy-CF = CF-Ph-CH = CHCH ₃ CH _{2 = CHCH 2 -Cy-CF =} CF-Ph-CH = CHCH 3 CH 3 C≡C-Cy-CF = CF-Ph-CH = CHCH 3 C 3 H 7 -Cy-CF = CF-PhF-CH = CHCH ₃ C ₃ H ₇ -Cy-CF = CF-Ph-CH = CHCH ₂ CH ₃

Example 4 Liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc. 80 wt%
To the liquid crystal composition, 20 wt% of the compound (E) -1- (4-chlorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in Example 1 was added. . Table 4 shows the liquid crystal properties of the obtained liquid crystal composition. As is clear from Table 4, the liquid crystal of the present invention
The composition has a high or One delta n low viscosity, high speed STN-type liquid crystal
It is useful as a liquid crystal composition for electro-optical elements .

Example 5 The compound (E) -1- (4- ( 1- propyne) obtained in Example 2 was used.
Nyl ) phenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene N-
The point I (T _c ) was 134.6 ° C. Further, 20 wt% of the compound of Example 2 was added to 80 wt% of the liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Inc. to give a liquid crystal composition. The liquid crystal properties of said liquid <br/> crystal composition shown in Table 5.

Examples 6 to 8 Liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc. 80 wt%
Then, 20 wt% of the compound obtained in Example 1 was added thereto to obtain a liquid crystal composition (Example 6). As comparative examples, a liquid crystal composition (Example 7 ) containing only the liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Ltd. and a liquid crystal composition "ZLI-1565" 80 wt.
% To (E) -1,2-difluoro-1,2-bis (4-
A liquid crystal composition (Example 8 ) containing 20 wt% of n-propylphenyl) ethylene was prepared. By sealing them in the liquid crystal cell with a polarizing plate was manufactured create a STN type liquid crystal display device.

[0086] The display characteristics of the liquid crystal display element of Example 6 and Example 8 are almost the same, high-speed response is obtained than a liquid crystal display device of Example 7. Then, ultraviolet rays using an ultraviolet carbon arc lamp in a liquid crystal display device of Example 6 and Example 8 50
Irradiated for 0 hours. After irradiation, the liquid crystal composition in each device was analyzed.

As a result , in the case of the liquid crystal composition of Example 6,
0.6% of (Z) -1- (4-chlorophenyl) -2-
(Trans-4-n-propylcyclohexyl) -1,
2-Difluoroethylene was produced. On the other hand , in the case of the liquid crystal composition of Example 8 , 6.3% (Z) -1,2-diflu
Oro-1,2-bis (4-n-propylphenyl) ethyl
The production of ren was confirmed.

Example 9 In place of (E) -1- (4-chlorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene obtained in Example 1 in Example 6 a, obtained in example 2 (E) -1- (4- ( 1- prop two
A liquid crystal display device was produced in the same manner as in Example 6 except that ( l ) phenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene was used . The
It was irradiated with ultraviolet rays to the liquid crystal display device, 0.5% (Z) -1- (4- (1- prop) phenyl) -2
-(Trans-4-n-propylcyclohexyl)-
1,2-difluoroethylene was produced.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

[0094]

Of the present invention, compounds tables in formula (1), the viscosity has decreased, and a large [Delta] n. But
Thus, when the compound of the present invention is used as a liquid crystal composition, a liquid crystal electro-optical device prepared by using the composition even if added in a small amount.
The element has an improved response speed . In addition , low voltage driving, high duty ratio driving, wide temperature range operation, etc. are possible.

Further, the compound of the present invention is more stable to ultraviolet light than the difluorostilbene type compound .
Therefore, the durability of the liquid crystal composition of the present invention is improved . Well
And, since the elastic coefficient (K ₃₃ / K ₁₁₎ increases, the high controller <br/> Las bets of. Since the liquid crystal upper limit temperature, that is, the NI point ( _Tc ) rises , the liquid crystal temperature range increases . Viscosity (η) decreases
Therefore, the compound of the present invention is advantageous for high-speed response .
Is a compound that improves each characteristic of the liquid crystal electro-optical element .

The compounds of the present invention are particularly high-speed STN type liquid crystals.
As an electro-optical element compound, difluorostilbene of
It has advantages over compound and is useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hidemasa Taka Inaka 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Keiko Oike 1150, Hazawa-machi, Kanagawa-ku, Yokohama Asahi Glass Central Research Institute Co., Ltd. (72) Inventor Jun Irizawa 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Institute (72) Inventor Sachi Machida 4-16-31 Okada, Samukawa-cho, Takaza-gun, Kanagawa (56) References JP-A-6-25030 (JP, A) JP-A-6-40967 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 22/08 C07C 25/24 C09K 19 / 30 G02F 1/13 500 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A difluoroethylene derivative compound represented by the following formula (1). R ^1- (A ¹ ) _m -Y ¹ -A ² -CF = CF-A ³ -Y ^2- (A ⁴ ) _n -R ² (1) However , in the formula (1), A ¹ , A ² , A ³ , A ⁴ , Y ¹ , Y ² ,
R ¹ , R ² , m and n are as follows. A ³ is a trans-1,4-cyclohexylene group, and A ¹ , A ² , A ⁴
Are independently of each other a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-cyclohexenylene group, and these ring groups are each unsubstituted.
Or having one or more halogen atoms or shea <br/> Ano group as a substituent, also one or more = CH- groups constituting a ring in these ring groups is substituted by a nitrogen atom well, one or more -CH ₂ - constituting the ring - group oxygen atom or may be substituted by a sulfur atom. Y ¹ and Y ² are independently of each other —COO—, —OCO—, —C≡C—, —CH ₂ CH ₂
-, - CH = CH -, - OCH 2 -, - shows a CH ₂ O- or a single bond. R ¹ and R ² independently have 1 to 1 carbon atoms.
0 alkyl group, or a halogen atom a cyano group,
In the case of the alkyl group, the carbon in the alkyl group - also between carbon bonded carbon between the alkyl group and the cyclic group - an oxygen atom between carbon bond, or carbonyl group is inserted oxycarbonyl group may have a carbon in the alkyl group of this - may be part of carbon bonds is a triple bond or double bond, of one of the alkyl groups of this -CH ₂ -
May group substituted by a carbonyl group, part of hydrogen atoms in the alkyl group of this or may have entirely substituted with a fluorine atom. In addition, at least one of R ^1, R ² are chlorine as or carbon atom - is a triple bond Moshiku part of carbon bonds is a group having a double bond. m and n independently represent 0 or 1. 2. The following formula ( 4 ) (wherein A ² in the formula ( 4 ):
A ³ , R ¹ and R ² are the same as those in formula (1) . Difluoro derivative compound of claim 1 represented by). R ¹ -A ² -CF = CF-A ³ -R ² ( 4 ) 3. A Jifuruo having liquid crystallinity selected from the difluoro derivative compound according to claim 1 or 2
Polyethylene derivative compound. 4. The method of claim 1, 2 or difluoro derivative compound a liquid crystal composition containing at least one according to 3. 5. sandwiching a liquid crystal composition according to between the electrodes with the substrate to 請 Motomeko 4 comprising a liquid crystal electro-optical element.