JPH05279278A - Trifluoroalkane derivative compound and liquid crystal composition - Google Patents

Abstract

PURPOSE:To provide the subject new compound exhibiting a low viscosity, excellent in stability and high-responsibility and useful for a liquid crystal display device, etc. CONSTITUTION:A compound of formula I (A<1> to A<4> are each a trans--1,4- disubstituted cyclohexylene, a 1,4-disubstituted phenylene, etc.; Y<1> and Y<2> are each COO, OCO, CidenticalC, CH2CH2, etc.; R<1> and R<2> are each a 1 to 10C alkyl, a halogen, cyano, etc.; m and n are each 0 or 1), e.g. a compound of formula II. In addition, the compound of formula I can be obtained by synthesizing a compound of formula IV from a compound of formula III as the raw material and reacting a fluorination agent such as diethylaminosulfate trifluoride therewith.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a trifluoroalkane derivative compound and a liquid crystal composition containing the same.

[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, there is no material satisfying all of these characteristics with a single material, and a plurality of liquid crystal and non-liquid crystal materials are mixed to satisfy the required performance as a liquid crystal composition. Therefore, it is desired to develop a liquid crystal or non-liquid crystal material that is excellent in one or two or more of all the characteristics.

[0004]

In the field of display devices using liquid crystals, it is desired to improve their performance, and low voltage driving, high definition display, high contrast ratio, wide viewing angle characteristics, low temperature response characteristics, wide operation are required. Temperature ranges and the like are desired, and any one of them tends to be sacrificed when the other is improved.

In particular, recently, low voltage driving and high speed response in battery drive, high definition display and high speed response in OA equipment, low temperature response in automobile display etc. or high speed response in wide operating temperature range have been made. It is desired to improve the response speed.

To solve this problem, some improvement methods can be considered. One of them is to adopt 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. Further, if the response speed is the same as that of the conventional one, it is possible to drive with a lower voltage or drive with a higher duty, that is, high-definition drive is possible.

For this purpose, a p, p'-disubstituted difluorostilbene compound as proposed at the 16th liquid crystal debate has been proposed. This compound has the general formula
It has a chemical structure as shown in (3).

[0008]

[Chemical 1]

However, R _A and R _{B in} the general formula (3) mean an n-alkyl group, an n-alkoxy group and an n-alkoxycarbonyl group.

The compound of the general formula (3) had low viscosity and improved stability to light as compared with a stilbene compound which was not substituted with fluorine. 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, a liquid crystal material having low viscosity and high stability to light has been desired.

[0012]

SUMMARY OF THE INVENTION The present invention provides a novel material for solving the above-mentioned problems and has a general formula:
(1) R ^1- (A ¹ ) _m -Y ¹ -A ² -CF ₂ CHF-A ³ -Y ^2- (A ⁴ ) _n -R ² (wherein A ^{1 to} A ⁴ are independent of each other. A trans-1,4-disubstituted cyclohexylene group or a 1,4-disubstituted phenylene group, each of which is unsubstituted or has one or more halogen or cyano groups as a substituent. 1 or 2 existing in these groups, which may have
One or more CH groups may be substituted with a nitrogen atom, Y ¹ ,
Y ² is independently of each other -COO-,-OCO-,-C≡C-,-CH ₂ CH ₂ -,-OCH
_2- , -CH ₂ O- or a single bond, m, n are 0 or 1, R ¹ and R ² are each independently a C 1-10 alkyl group, a halogen, a cyano group. In the case of an alkyl group, an oxygen atom may be inserted between the carbon-carbon bond or between the carbon-carbon bond between this group and the ring, and a part of the carbon-carbon bond has a double bond. It may be a bond, or one of the —CH ₂ — groups may be substituted with a carbonyl group, and some or all of the hydrogen atoms in the group may be substituted with a fluorine atom. It may be represented by the formula).

The general formula (2) R ¹ -A ² -CF ₂ CHF-A ³ -R ² (in the formula, A ² , A ³ , R ¹ and R ² are the same as above) And a trifluoroalkane derivative compound represented by the general formula (1) or general formula (2)
The present invention provides a liquid crystal composition containing a compound represented by:

The compound of the general formula (1) of the present invention has a relatively small refractive index anisotropy (Δn), low viscosity,
In addition, it is a material that has excellent compatibility with other liquid crystals or non-liquid crystals and is chemically stable, particularly, stable to light.

Specific structures of the compound of the present invention include the following compounds. As typical compounds thereof, there are the following compounds as compounds having two rings. R ¹ -A ² -CF ₂ CHF-A ³ -R ² (2)

More specifically, the compound of the general formula (2) includes the following compounds. In the following description, not only the compound of the general formula (2), but "-Ph-" is 1,
Represents a 4-disubstituted phenylene group, "-Cy-" is trans-1,4
Represents a di-substituted cyclohexylene group. R ¹ -Ph-CF ₂ CHF-Ph-R ² (2A)

[0017]

[Chemical 2]

The following compounds are examples of compounds in which one or two of the 1,4-di-substituted phenylene groups are replaced with trans-1,4-di-substituted cyclohexylene groups. R ¹ -Cy-CF ₂ CHF-Ph-R ² (2B) R ¹ -Ph-CF ₂ CHF-Cy-R ² (2C) R ¹ -Cy-CF ₂ CHF-Cy-R ² (2D)

Further, there are the following compounds as a compound in which the 1,4-disubstituted phenylene group is a phenylene group in which some hydrogen atoms are replaced by fluorine atoms. R ¹ -Ph-CF ₂ CHF-PhF-R ² (2E)

[0020]

[Chemical 3]

Further, as a compound having three rings, there are the following compounds. R ¹ -A ¹ -A ² -CF ₂ CHF-A ³ -R ² (4) R ¹ -A ² -CF ₂ CHF-A ³ -A ⁴ -R ² (5)

More specifically, the compound of the general formula (5) includes the following compounds. R ¹ -Ph-Ph-CF ₂ CHF-Ph-R ² (4A) R ¹ -Ph-CF ₂ CHF-Ph-Ph-R ² (5A)

[0023]

[Chemical 4]

One of the 1,4-disubstituted phenylene groups, 2
Examples of compounds in which one or three of them are substituted with a trans-1,4-di-substituted cyclohexylene group include the following compounds. R ¹ -Cy-Ph-CF ₂ CHF-Ph-R ² (4B) R ¹ -Ph-Cy-CF ₂ CHF-Ph-R ² (4C) R ¹ -Ph-Ph-CF ₂ CHF-Cy-R ² (4D) R ¹ -Cy-Cy-CF ₂ CHF-Ph-R ² (4E) R ¹ -Cy-Ph-CF ₂ CHF-Cy-R ² (4F) R ¹ -Ph-Cy-CF ₂ CHF -Cy-R ² (4G) R ¹ -Cy-Cy-CF ₂ CHF-Cy-R ² (4H)

R ¹ -Cy-CF ₂ CHF-Ph-Ph-R ² (5B) R ¹ -Ph-CF ₂ CHF-Cy-Ph-R ² (5C) R ¹ -Ph-CF ₂ CHF-Ph- Cy-R ² (5D) R ¹ -Cy-CF ₂ CHF-Cy-Ph-R ² (5E) R ¹ -Cy-CF ₂ CHF-Ph-Cy-R ² (5F) R ¹ -Ph-CF ₂ CHF-Cy-Cy-R ² (5G) R ¹ -Cy-CF ₂ CHF-Cy-Cy-R ² (5H)

Further, there is the following compound as a compound in which the 1,4-disubstituted phenylene group is a phenylene group in which some hydrogen atoms are replaced by fluorine atoms. R ¹ -Ph-Ph-CF ₂ CHF-PhF-R ² (4I) R ¹ -Ph-CF ₂ CHF-Ph-PhF-R ² (5I)

Further, there are the following compounds as compounds having four rings. R ¹ -A ¹ -A ² -CF ₂ CHF-A ³ -A ⁴ -R ² (6)

More specifically, the compound of the general formula (5) includes the following compounds. R ¹ -Ph-Ph-CF ₂ CHF-Ph-Ph-R ² (6A)

[0029]

[Chemical 5]

R ¹ -Cy-Ph-CF ₂ CHF-Ph-Ph-R ² (6B) R ¹ -Cy-Ph-CF ₂ CHF-Ph-Cy-R ² (6C) R ¹ -Ph-Cy- CF ₂ CHF-Ph-Ph-R ² (6D) R ¹ -Ph-Ph-CF ₂ CHF-Cy-Ph-R ² (6E) R ¹ -Ph-Ph-CF ₂ CHF-Ph-PhF-R ² (6F) R ¹ -Ph-Ph-CF ₂ CHF-PhF-Ph-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-COO-Ph-CF ₂ CHF-Ph-R ² (4J) R ¹ -Ph-OCO-Ph-CF ₂ CHF-Ph-R ² (4K) R ¹ -Ph-C ≡ C-Ph-CF ₂ CHF-Ph-R ² (4L) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF ₂ CHF-Ph-R ² (4M) R ¹ -Ph-OCH ₂ -Ph-CF ₂ CHF-Ph-R ² (4N) R ¹ -Ph-CH ₂ O-Ph-CF ₂ CHF-Ph-R ² (4O)

R ¹ -Ph-CF ₂ CHF-Ph-COO-Ph-R ² (5J) R ¹ -Ph-CF ₂ CHF-Ph-OCO-Ph-R ² (5K) R ¹ -Ph-CF ₂ CHF-Ph-C ≡ C-Ph-R ² (5L) R ¹ -Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-R ² (5M) R ¹ -Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-R ² (5N) R ¹ -Ph-CF ₂ CHF-Ph-CH ₂ O-Ph-R ² (5O)

R ¹ -Ph-COO-Ph-CF ₂ CHF-Ph-Ph-R ² (6H) R ¹ -Ph-OCO-Ph-CF ₂ CHF-Ph-Ph-R ² (6I) R ^1- Ph-C ≡ C-Ph-CF ₂ CHF-Ph-Ph-R ² (6J) R ¹ -Ph-CH ₂ CH ₂ -Ph-CF ₂ CHF-Ph-Ph-R ² (6K) R ¹ -Ph -OCH ₂ -Ph-CF ₂ CHF-Ph-Ph-R ² (6L) R ¹ -Ph-CH ₂ O-Ph-CF ₂ CHF-Ph-Ph-R ² (6M) R ¹ -Ph-COO- Ph-CF ₂ CHF-Ph-OCO-Ph-R ² (6N)

There are also the following compounds in which the groups A ^{1 to} A ⁴ are groups having a ring structure other than the 1,4-di-substituted phenylene group and the trans-1,4-di-substituted cyclohexylene group. ..

[0036]

[Chemical 6]

By mixing the above-mentioned compound of the present invention with another liquid crystal material or a non-liquid crystal material to form a liquid crystal composition, the liquid crystal composition can have a low viscosity and can be used as a liquid crystal display device. In that case, high-speed response becomes possible.

The compound of the formula (1) of the present invention is used as a liquid crystal composition by mixing at least one kind with other liquid crystal and non-liquid crystal.

Examples of substances to be mixed with the compound of the present invention are as follows. In the formula below, R _C and R _D are an alkyl group, an alkoxy group, a halogen atom,
Represents a group such as a cyano 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

[0043]

[Chemical 7]

These compounds are merely examples, and the substitution of a hydrogen atom of a ring structure or a terminal group with a halogen atom, a cyano group, a methyl group, etc., a cyclohexane ring, another six-membered ring of a benzene ring, and a pentagonal ring. Substitution with a member ring or the like, change of a bonding group between the rings, and the like are possible, and various materials may be selected and used according to desired performance.

The composition of the present invention is disposed as a liquid crystal composition between substrates with electrodes, and is a twisted nematic system, a guest-host system, a dynamic scattering system, a phase change system, a DAP system, a dual frequency drive system, It can be used in various modes such as a ferroelectric liquid crystal display system.

Specifically, the followings are typical. If necessary, on a substrate such as plastic or glass
SiO ₂ , Al ₂ O ₃ etc. undercoat layer or color filter layer is formed, In ₂ O ₃ -SnO ₂ (ITO), SnO ₂ etc. electrodes are provided, and after patterning, polyimide, polyamide as required , SiO ₂ , Al ₂ O ₃ etc. are formed, orientation treatment is applied, printing sealing material is printed on this, sealing the periphery by arranging so that the electrode surfaces face each other, and hardening the sealing material. To form an empty cell.

A composition containing the compound of the present invention is injected into this empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. A polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflection plate, a reflection plate, if necessary, for this liquid crystal cell.
Laminated light guide plate, UV cut filter, etc., letters,
A liquid crystal display element is obtained by printing a figure or the like or performing non-glare processing.

The above description merely shows the basic structure and manufacturing method of the liquid crystal display element, for example, a substrate using a two-layer electrode, a two-layer liquid crystal cell in which two liquid crystal layers are formed,
Various structures such as an active matrix element using an active matrix substrate on which active elements such as TFT and MIM are formed can be used.

By using the compound of the present invention in a liquid crystal composition, a high speed response can be expected even when high duty driving is performed. Therefore, it is also suitable for a super twist (STN) type liquid crystal display element having a high twist angle, which has been receiving attention in recent years.

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

However, in the above formula, A ^{1 to} A ⁴ are each independently a 1,4-disubstituted phenylene group, and each of these groups is unsubstituted or has one or two substituents. It may have one or more halogens, and one or two or more CH groups present in these groups may be substituted with a nitrogen atom. Y ¹ and Y ² are independent of each other -COO-,
-OCO- or a single bond, m, n represents 0 or 1,
R ¹ and R ² each independently represent a perfluoroalkyl group having 1 to 10 carbon atoms, a perfluoroalkoxy group, a halogen or a cyano group.

That is, a benzyl ketone derivative compound represented by the general formula (7) is reacted with chlorine gas at a high temperature to obtain a dichlorobenzyl ketone compound (8), which is then converted into fluorine such as potassium fluoride or hydrogen fluoride. A difluorobenzyl ketone compound (9) is obtained by reacting with an agent. Then this formula
The hydroxy compound (10) is obtained by reacting the compound of (9) with a reducing agent such as sodium borohydride.
Then, by reacting with a fluorinating agent diethylaminosulfur trifluoride (DAST), a compound of the general formula
The trifluoroalkane derivative compound (1) can be obtained.

[0053] Further, the method of introducing the R ^1, R ² an acyl group of the general formula (1) in this method, the general formula R ^1, R ² is hydrogen (1)
The Friedel-Crafts reaction of the compound of 1 with an acyl halide may be used. In addition, the method of introducing a cyano group,
A compound of the general formula (1) in which R ¹ and R ² are bromine or iodine is
It can be reacted with CuCN. Further, the method of introducing an alkyl group, R ¹ , R ² is a compound of the general formula (1) is chlorine or bromine, and an organometallic compound prepared from an alkyl halide, Ni, Pd in the presence of a catalyst such as Pd Just let it ring.

The dichlorobenzyl ketone compound represented by the general formula (8) can also be produced by the following production method.

However, in the above formula, A ^{1 to} A ⁴ are independently of each other a trans-1,4-disubstituted cyclohexylene group or a 1,4-disubstituted phenylene group, and these groups are each a non-group. It may be substituted or may have one or two or more halogens as a substituent, and one or two or more CH groups present in these groups may be substituted with a nitrogen atom. ..

Y ¹ and Y ² are independently of each other --COO--, --OCO--, --C≡
C-,-CH ₂ CH ₂ -,-OCH ₂ -,-CH ₂ O- or represents a single bond, m, n
Represents 0 or 1, and R ¹ and R ² are independently of each other the number of carbon atoms.
1-10 alkyl group, halogen or cyano group are shown, and in the case of an alkyl group, an oxygen atom may be inserted between carbon-carbon bonds or between carbon-carbon bonds between this group and the ring. Further, a part of the carbon-carbon bond may be a double bond, and a part or all of hydrogen atoms in the group may be replaced with a fluorine atom.

That is, the diketone compound of the general formula (11) is treated with a chlorinating agent such as phosphorus pentachloride to give the dichloroketone compound.
Then, the compound of the general formula (1) is obtained by the same step as above.

[0058] Further, the method of introducing the R ^1, R ² an acyl group of the general formula (1) in this method, the general formula R ^1, R ² is hydrogen (1)
The Friedel-Crafts reaction of the compound of 1 with an acyl halide may be used. In addition, the method of introducing a cyano group,
A compound of the general formula (1) in which R ¹ and R ² are bromine or iodine is
It can be reacted with CuCN. These manufacturing methods are merely examples, and various manufacturing methods can be used.

[0059]

【Example】

Example 1 In a 100 ml glass three-necked flask equipped with a reflux tube and a gas injection tube, 26.5 g (0.4%) of 4,4'-dichlorobenzyl phenyl ketone was added.
1 mol) was charged and heated to 150 ° C. Cl ₂ gas here
71 g, bubbling over 3 hours keeping the reaction temperature at 150-170 ° C. After cooling, 50 ml of methylene chloride was added, washed with water, the organic layer was separated, dried and the solvent was distilled off to obtain α,
32.7 g of α, 4,4'-tetrachlorobenzyl phenyl ketone
(Yield 98%) was obtained. Cl-Ph-CCl ₂ CO-Ph-Cl

[0060]

[Chemical 8]

32.7 g of α, α, 4,4'-tetrachlorobenzyl phenyl ketone obtained in a 100 ml glass three-necked flask equipped with a reflux tube and spray-dried potassium fluoride were added.
13.6 g was added. The mixture was reacted at 220 ° C for 2 hours with vigorous stirring. After cooling, methylene chloride was added, the inorganic salt was filtered off, the filtrate was washed with water, the solvent was distilled off, and the obtained solid was recrystallized from methyl alcohol to obtain α, α-difluoromethane.
19.2 g of -4,4'-dichlorobenzyl phenyl ketone (yield
65%) obtained. Cl-Ph-CF ₂ CO-Ph-Cl

[0062]

[Chemical 9]

Then, 6.02 g (0.02 mol) of α, α-difluoro-4,4'-dichlorobenzyl phenyl ketone and 30 ml of dry ethyl alcohol obtained were charged in a 100 ml three-necked flask, and sodium borohydride was added at 0 ° C. 0.76 g (0.02
mol) was added, and the mixture was further stirred at room temperature for 2 hours. After adding water and extracting with methylene chloride, the organic layer was washed with water and the solvent was distilled off to give 1,1-difluoro-2-hydroxy-1,2-bis (4-
5.76 g (yield 95%) of chlorophenyl) ethane was obtained. Cl-Ph-CF ₂ CHOH-Ph-Cl

[0064]

[Chemical 10]

Then, 5.76 g of the obtained 1,1-difluoro-2-hydroxy-1,2-bis (4-chlorophenyl) ethane was dissolved in 30 ml of dry methylene chloride, and 6.12 g of diethylaminosulfur trifluoride (DAST) was dissolved. (0.038 mol) was added. After stirring at room temperature for 24 hours, water was added and the mixture was extracted with methylene chloride. After washing the organic layer with water, the solvent was distilled off, and the obtained crude crystals were purified by silica gel column chromatography.
4.88 g (yield 84%) of 1,1,2-trifluoro-1,2-bis (4-chlorophenyl) ethane was obtained. Cl-Ph-CF ₂ CHF-Ph-Cl

[0066]

[Chemical 11]

The analysis results of this compound are shown below. ¹⁹ F NMR (CDCl ₃ ) -106.8ppm (1F, m), -108.6ppm (1F, m),
-190.7ppm (1F, m) MS m / e 305 (M ⁺ ) IR 1230cm ^-1 (CF)

Example 2 Under an argon atmosphere, 1.92 g (0.08 mol) of magnesium and 20 ml of dry tetrahydrofuran (THF) were placed in a 100 ml three-necked flask equipped with a reflux tube, and a few drops of 1-bromopropane were added thereto. Then, 8.85 g (0.072 mol) of 1-bromopropane is added dropwise at a rate at which heat generation continues. After the addition is complete, continue refluxing for another hour and allow to cool to room temperature. This solution was separately put into a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere to obtain 1,1,2-trifluoro-1,2-obtained in Example 1.
Bis (4-chlorophenyl) ethane 3.66 g (0.012 mol) and
20 ml of dry THF solution containing 0.2 g of 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl ₂ (dppp)]
Then, add dropwise using a dropping funnel.

After the dropwise addition, the mixture was refluxed for another 6 hours, cooled to room temperature, and 20 ml of water was added. Further, 20 ml of 1N hydrochloric acid is added to separate the organic layer, which is washed with water and dried, and then the solvent is distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.69 g (yield 70%) of 1,1,2-trifluoro-1,2-bis (4-n-propylphenyl) ethane. .. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-C ₃ H ₇ (n)

[0070]

[Chemical 12]

The analysis results of this compound are shown below. MS m / e 320 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 2. CH ₃ -Ph-CF ₂ CHF-Ph-CH ₃ nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-C ₅ H ₁₁ (n) nC ₇ H ₁₅ -Ph-CF ₂ CHF-Ph-C ₇ H ₁₅ (n) nC ₁₀ H ₂₁ -Ph-CF ₂ CHF-Ph-C ₁₀ H ₂₁ (n)

Example 3 12.7 g (0.072 m) of trans-1-bromo-4-methylcyclohexane was used instead of 1-bromopropane used in Example 2.
ol) The reaction was performed in the same manner as in Example 2 except that 1,1,2-
3.53 g (yield 72%) of trifluoro-1,2-bis [4- (trans-4-methylcyclohexyl) phenyl] ethane was obtained. CH ₃ -Cy-Ph-CF ₂ CHF-Ph-Cy-CH ₃

[0074]

[Chemical 13]

The analysis results of this compound are shown below. MS m / e 408 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 3. nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-Cy-C ₃ H ₇ (n) nC ₅ H ₁₁ -Cy-Ph-CF ₂ CHF-Ph-Cy-C ₅ H ₁₁ (n) CH ₃ -Ph-Ph-CF ₂ CHF-Ph-Ph-CH ₃ nC ₃ H ₇ -Ph-Ph-CF ₂ CHF-Ph-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -Ph-Ph-CF ₂ CHF-Ph-Ph-C ₅ H ₁₁ (n)

Example 4 Instead of 4,4'-di (n-propyl) benzylphenylketone used in Example 1, 33.2 g (0.1 mol) of 4,4'-bis (trifluoromethyl) benzylphenylketone was used. ) Is the same as in Example 1, except that 1,1,2-trifluoro-
1,2-bis (4-trifluoromethylphenyl) ethane
Obtained 5.95 g. CF ₃ -Ph-CF ₂ CHF-Ph-CF ₃

[0078]

[Chemical 14]

The analysis results of this compound are shown below. MS m / e 372 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 4. nC ₃ F ₇ -Ph-CF ₂ CHF-Ph-C ₃ F ₇ (n) nC ₅ F ₁₁ -Ph-CF ₂ CHF-Ph-C ₅ F ₁₁ (n) CF ₃ -Ph-Ph-CF ₂ CHF -Ph-Ph-CF ₃ nC ₃ F ₇ -Ph-Ph-CF ₂ CHF-Ph-Ph-C ₃ F ₇ (n)

Example 5 A 100 ml glass three-necked flask equipped with a reflux tube was charged with 4-n-propylphenyl- (trans-4-methylcyclohexyl) diketone 54.4 g (0.20 mol) and phosphorus pentachloride 83.2 g (0.4 mol). The mixture was reacted at 140 ° C for 6 hours. After cooling, water and methylene chloride were added, the organic layer was separated, and the aqueous layer was extracted with methylene chloride. The organic layers are combined, washed with water, dried, and the solvent is evaporated to remove 4- (n-propyl) -α, α-dichlorobenzyl.
58.9 g of-(trans-4-methylcyclohexyl) ketone
(Yield 90%) was obtained.

58.9 g of 4- (n-propyl) -α, α-dichlorobenzyl- (trans-4-methylcyclohexyl) ketone obtained in a 100 ml glass three-necked flask equipped with a reflux tube.
And 25.1 g of spray-dried potassium fluoride was added.
The mixture was reacted at 220 ° C for 3 hours with vigorous stirring. After cooling, methylene chloride was added, the inorganic salt was filtered off, the filtrate was washed with water, the solvent was distilled off, and the obtained solid was recrystallized from methyl alcohol to give 4- (n-propyl) -α, α. -31.8 g (yield 60%) of difluorobenzyl- (trans-4-methylcyclohexyl) ketone was obtained.

Then, 5.88 g (0.02 mol) of 4- (n-propyl) -α, α-fluorobenzyl- (trans-4-methylcyclohexyl) ketone obtained in a 100 ml three-necked flask was obtained.
Then, 30 ml of dry ethyl alcohol was charged, 0.76 g (0.02 mol) of sodium borohydride was added at 0 ° C., and the mixture was further stirred at room temperature for 2 hours. After adding water and extracting with methylene chloride, washing the organic layer with water, distilling off the solvent, 1,1-difluoro
5.62 g of 2-hydroxy-1- (trans-4-methylcyclohexyl) -2- (n-propylphenyl) ethane (yield 95
%)Obtained.

Then, the obtained 1,1-difluoro-2-hydroxy-1- (trans-4-methylcyclohexyl) -2- (n-
Propylphenyl) ethane 5.62 g dry methylene chloride 30
Dissolve in ml and diethylaminosulfur trifluoride
6.12 g (0.038 mol) of (DAST) was added. After stirring at room temperature for 24 hours, water was added and the mixture was extracted with methylene chloride. After washing the organic layer with water, the solvent was distilled off, and the resulting crude crystals were purified by silica gel column chromatography to give 1,1,2-trifluoro-1-
4.87 g (yield 86%) of (trans-4-methylcyclohexyl) -2- (4-n-propylphenyl) ethane was obtained. CH ₃ -Cy-CF ₂ CHF-Ph-C ₃ H ₇ (n)

[0085]

[Chemical 15]

The analysis results of this compound are shown below. MS m / e 298 (M ⁺ ) IR 1230cm ^-1 (CF)

Example 6 4-n-propylphenyl- (trans-4-used in Example 5
Instead of methylcyclohexyl) diketone, bis (4-
(Methoxyphenyl) diketone was reacted in the same manner as in Example 5 except that 54.0 g (0.2 mol) of 1,1,2-trifluoro was used.
4.74 g of -1,2-bis (4-methoxyphenyl) ethane was obtained. CH ₃ O-Ph-CF ₂ CHF-Ph-OCH ₃

[0088]

[Chemical 16]

The analysis results of this compound are shown below. MS m / e 296 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Examples 5 and 6. CH ₃ -Cy-CF ₂ CHF-Ph-C ₅ H ₁₁ (n) CH ₃ -Cy-CF ₂ CHF-Ph-C ₇ H ₁₅ (n) CH ₃ -Cy-CF ₂ CHF-Ph-C ₁₀ H ₂₁ (n) CH ₃ O-Cy-CF ₂ CHF-Ph-C ₃ H ₇ (n) nC ₃ H ₇ O-Cy-CF ₂ CHF-Ph-C ₃ H ₇ (n)

NC ₃ H ₇ O-Ph-CF ₂ CHF-Ph-OC ₃ H ₇ (n) nC ₅ H ₁₁ O-Ph-CF ₂ CHF-Ph-OC ₅ H ₁₁ (n) nC ₁₀ H ₂₁ O -Ph-CF ₂ CHF-Ph-OC ₁₀ H ₂₁ (n)

Example 7 4-n-propylphenyl- (trans-4-used in Example 5
4-n-propylphenyl- (5-methylpyrimidinyl) diketone was replaced by 69.6 instead of methylcyclohexyl) diketone.
Reaction was carried out in the same manner as in Example 5 except that g (0.2 mol) was used.
1,1,2-trifluoro-1- (5-methylpyrimidinyl) -2- (4-n
-Propylphenyl) ethane was obtained 4.70 g. CH ₃ -Py-CF ₂ CHF-Ph-OC ₃ H ₇ (n)

[0093]

[Chemical 17]

The analysis results of this compound are shown below. MS m / e 294 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 7. nC ₃ H ₇ -Py-CF ₂ CHF-Ph-OCH ₃ nC ₅ H ₁₁ -Py-CF ₂ CHF-Ph-CH ₃ nC ₇ H ₁₅ -Py-CF ₂ CHF-Ph-OC ₃ H ₇ (n) nC ₃ H ₇ -Py-CF ₂ CHF-Cy-OCH ₃ nC ₃ H ₇ -Py-CF ₂ CHF-Cy-CH ₃

Example 8 4-n-propylphenyl- (trans-4-used in Example 5
Instead of methylcyclohexyl) diketone, bis (3-
54.8 g (0.2 mo of fluoro-4-methylphenyl) diketone
l) The reaction is carried out in the same manner as in Example 5 except that 1,1,2-
4.80 g of trifluoro-1,2-bis (3-fluoro-4-methylphenyl) ethane was obtained. CH ₃ -PhF-CF ₂ CHF-PhF-CH ₃

[0097]

[Chemical 18]

The analysis results of this compound are shown below. MS m / e 300 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 8. CH ₃ O-PhF-CF ₂ CHF-PhF-OCH ₃ nC ₃ H ₇ -PhF-CF ₂ CHF-PhF-C ₃ H ₇ (n) nC ₃ H ₇ O-PhF-CF ₂ CHF-PhF-OC ₃ H ₇ (n) nC ₅ H ₁₁ -PhF-CF ₂ CHF-PhF-C ₅ H ₁₁ (n) nC ₇ H ₁₅ -PhF-CF ₂ CHF-PhF-C ₇ H ₁₅ (n)

Example 9 4-n-propylphenyl- (trans-4-used in Example 5
The reaction was performed in the same manner as in Example 5 except that 69.6 g (0.2 mol) of 4-n-propylphenyl- [4- (trans-4-methylcyclohexyl) phenyl] diketone was used instead of methylcyclohexyl) diketone, and 1 , 1,2-trifluoro-1-
[4- (trans-4-methylcyclohexyl) phenyl] -2-
5.04 g of (4-n-propylphenyl) ethane was obtained. CH ₃ -Cy-Ph-CF ₂ CHF-Ph-C ₃ H ₇ (n)

[0101]

[Chemical 19]

The analysis results of this compound are shown below. MS m / e 374 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 9. nC ₅ H ₁₁ -Cy-Ph-CF ₂ CHF-Ph-CH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-OCH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-OC ₃ H ₇ (n) nC ₃ H ₇ -Ph-Ph-CF ₂ CHF-Ph-C ₃ H ₇ (n)

Example 10 4-n-propylphenyl- (trans-4-used in Example 5
Instead of methyl cyclohexyl) diketone, 69.6 g (0.) of 4-n-propylphenyl- (4-bromophenyl) diketone.
2mol) The reaction was performed in the same manner as in Example 5 except that 1,1,1,
5.70 g of 2-trifluoro-1- (4-n-propylphenyl) -2- (4-bromophenyl) ethane was obtained.

Then, 0.72 g (0.008 mol) of CuCN was dissolved in 25 ml of anhydrous dimethyl sulfoxide (DMSO) by heating at 90 ° C. and dissolved, and the resulting 1,1,2-trifluoro-1- (4 -n-Propylphenyl) -2- (4-bromophenyl) ethane 2.85g
(0.008 mol) DMSO solution is added dropwise. Then further
After stirring at 150 ° C for 1 hour, cool to room temperature. 100 ml of water
Is poured, the mixture is extracted with methylene chloride, the organic layer is washed with saturated brine and dried over CaCl ₂ . After filtration, the solvent was evaporated, the obtained solid was purified by silica gel column chromatography, and 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- (4-cyanophenyl ) 2.18 g of ethane was obtained. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-CN

[0106]

[Chemical 20]

The analysis results of this compound are shown below. MS m / e 303 (M ⁺ ) IR 1230cm ^-1 (CF), 2230cm ^-1 (C≡N)

The following compounds can be obtained in the same manner as in Example 10. CH ₃ -Ph-CF ₂ CHF-Ph-CN CH ₃ -Cy-CF ₂ CHF-Ph-CN nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-CN nC ₃ H ₇ -Cy-Ph-CF ₂ CHF -Ph-CN nC ₃ H ₇ -Ph-Ph-CF ₂ CHF-Ph-CN nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-Ph-CN

Example 11 1.85 g (0.0) of 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- (4-bromophenyl) ethane prepared in Example 10
08mol), and 4.77 g of 4-methylphenethyl bromide.
(0.024 mol) and magnesium were used in the same manner as in Example 2 except that 0.64 g (0.026 mol) was used, and 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- [4 1.90 g (yield 60%) of-(4-methylphenethyl) phenyl] ethane was obtained. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-CH ₃

[0110]

[Chemical 21]

The analysis results of this compound are shown below. MS m / e 396 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 11. CH ₃ -Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-CH ₃ nC ₃ H ₇ O-Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-CH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-CH ₃ CH ₃ -Ph-Ph -CF ₂ CHF-Ph-CH ₂ CH ₂ -Ph-CH ₃

Example 12 4-n-propylphenyl- (trans-4-used in Example 5
Instead of (methylcyclohexyl) diketone, 75.6 g (0.) of 4-n-propylphenyl- (4-iodophenyl) diketone.
2mol) The reaction was performed in the same manner as in Example 5 except that 1,1,1,
6.45 g of 2-trifluoro-1- (4-n-propylphenyl) -2- (4-iodophenyl) ethane was obtained.

Under an argon atmosphere, 0.69 g of cuprous iodide and 6.45 g of 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- (4-iodophenyl) ethane were placed in a 100 ml three-necked flask.
(0.016 mol) and 30 ml of anhydrous THF are charged and stirred at room temperature. To this are added 1.80 ml of n-butylamine and 2.62 g of p-toluylacetylene. Then, (Ph ₃ P) ₄ Pd 0.70g
10 ml of anhydrous THF solution containing is added and stirred at room temperature for 2 hours. After adding 30 ml of saturated NaHCO ₃ water and separating the layers, the mixture is extracted with methylene chloride. After the solvent was distilled off, the residue was purified by silica gel column chromatography and then 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- [4- (2-P-toluylethynyl) phenyl]
4.52 g (yield 72%) of ethane was obtained. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-C ≡ C-Ph-CH ₃

[0115]

[Chemical formula 22]

The analysis results of this compound are shown below. MS m / e 396 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 12. CH ₃ -Ph-CF ₂ CHF-Ph-C ≡ C-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-C ≡ C-Ph-CH ₃ nC ₃ H ₇ O -Ph-CF ₂ CHF-Ph-C≡C-Ph-CH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-C≡C-Ph-CH ₃ CH ₃ -Ph-Ph-CF ₂ CHF -Ph-C ≡ C-Ph-CH ₃

Example 13 4-n-propylphenyl- (trans-4-used in Example 5
The reaction was performed in the same manner as in Example 5 except that 62.4 g (0.2 mol) of 4-n-propylphenyl- (4-methoxymethyloxyphenyl) diketone was used instead of methylcyclohexyl) diketone, and then treated with an acid. 1,1,2-trifluoro-1- (4-
4.69 g of n-propylphenyl) -2- (4-hydroxyphenyl) ethane was obtained.

Then, the obtained 1,1,2-trifluoro-1-
(4-n-Propylphenyl) -2- (4-hydroxyphenyl)
2.34 g (0.008 mol) of ethane, 1.22 g of potassium carbonate and 30 ml of acetone were added, and 1.63 g of α-bromo-p-xylene was added dropwise at room temperature. Reflux for 4 hours, then cool,
After filtration, the solvent was evaporated, the obtained crude crystals were purified by silica gel column chromatography, and 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- [4- ( 2.87 g (yield 90%) of 4-methylbenzyloxy) phenyl] ethane was obtained. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-CH ₃

[0120]

[Chemical formula 23]

The analysis results of this compound are shown below. MS m / e 398 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 13. CH ₃ -Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-CH ₃ nC ₃ H ₇ O-Ph -CF ₂ CHF-Ph-OCH ₂ -Ph-CH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-CH ₃ CH ₃ -Ph-Ph-CF ₂ CHF-Ph-OCH ₂ -Ph-CH ₃

Example 14 2.34 g of 1,1,2-trifluoro-1- (4-n-propylphenyl) -2- (4-hydroxyphenyl) ethane prepared in Example 13
(0.008 mol) was dissolved in 10 ml of CH ₂ Cl ₂ , 0.70 g (0.009 mol) of pyridine was added at room temperature, and after cooling to 0 ° C, p-
1.36 g (0.009 mol) of toluic acid chloride was added dropwise. Stir at room temperature for 1 hour, cool, add dilute hydrochloric acid, filter,
The crude crystals obtained by distilling off the solvent were purified by silica gel column chromatography to obtain 1,1,2-trifluoro-1- (4-
3.10 g (94% yield) of n-propylphenyl) -2- [4- (4-methylbenzoyloxy) phenyl] ethane was obtained. nC ₃ H ₇ -Ph-CF ₂ CHF-Ph-OCO-Ph-CH ₃

[0124]

[Chemical formula 24]

The analysis results of this compound are shown below. MS m / e 412 (M ⁺ ) IR 1230cm ^-1 (CF)

The following compounds can be obtained in the same manner as in Example 14. CH ₃ -Ph-CF ₂ CHF-Ph-OCO-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -Ph-CF ₂ CHF-Ph-OCO-Ph-CH ₃ nC ₃ H ₇ O-Ph-CF ₂ CHF-Ph-OCO-Ph-CH ₃ nC ₃ H ₇ -Cy-Ph-CF ₂ CHF-Ph-OCO-Ph-CH ₃ CH ₃ -Ph-Ph-CF ₂ CHF-Ph-OCO-Ph-CH ₃

Example 15 A liquid crystal composition was prepared by adding 2.5 wt% of the compound of Example 1 of the present invention to 97.5 wt% of the liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Inc. When the viscosity was examined, the viscosity was lower than that of the conventional example (only the liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Inc.). This decrease in viscosity was almost the same as when the difluorostilbene type liquid crystal having a similar structure was added, and the deterioration with respect to ultraviolet rays was less than that of the difluorostilbene type liquid crystal.

[0128]

The general formula (1) R ^1- (A ¹ ) _m -Y ¹ -A ² -CF ₂ CHF-A ³ -Y ^2- (A ⁴ ) _n -R ² (A ¹ ~ The compounds represented by A ⁴ , R ¹ , R ² , Y ¹ , Y ² , m, and n have the above-mentioned meanings) and have a low viscosity. Is a low voltage drive, high duty drive,
Wide temperature range operation is possible.

Further, the durability against ultraviolet rays and the like is higher than that of the difluorostilbene type liquid crystal, and the characteristic of its low viscosity can be fully utilized.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 69/74 Z 9279-4H 69/75 A 9279-4H 69/753 D 9279-4H 69/757 C 9279-4H 69/773 9279-4H 69/86 9279-4H 69/92 9279-4H 69/94 9279-4H 255/46 6917-4H 255/54 6917-4H 255/55 6917-4H 255/57 6917 −4H C09K 19/14 7457-4H 19/18 7457-4H 19/20 7457-4H 19/30 7457-4H (72) Inventor Takashi Miyajima 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. (72) Inventor Hidemasa Taka 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture G.Technology Co., Ltd. (72) Inventor, Masaru Machida 4-16-31 Okada, Samukawa-cho, Takaza-gun, Kanagawa Prefecture

Claims (3)

[Claims] 1. A general formula (1) R ^1- (A ¹ ) _m -Y ¹ -A ² -CF ₂ CHF-A ³ -Y ^2- (A ⁴ ) _n -R ² (wherein A ¹ ~ A ⁴ is, independently of each other, a trans-1,4-di-substituted cyclohexylene group or a 1,4-di-substituted phenylene group, each of which is unsubstituted or has 1 or 2 substituents. It may have the above halogen or cyano group, and one or two existing in these groups.
One or more CH groups may be substituted with a nitrogen atom, Y ¹ ,
Y ² is independently of each other -COO-,-OCO-,-C≡C-,-CH ₂ CH ₂ -,-OCH
₂ -,-CH ₂ O- or a single bond, m and n represent 0 or 1, and R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, a halogen or a cyano group. In the case of an alkyl group, an oxygen atom may be inserted between the carbon-carbon bond or between the carbon-carbon bond between this group and the ring, and a part of the carbon-carbon bond has a double bond. It may be a bond, or one of the —CH ₂ — groups may be substituted with a carbonyl group, and some or all of the hydrogen atoms in the group may be substituted with a fluorine atom. May be represented). 2. A general formula (2) R ¹ -A ² -CF ₂ CHF-A ³ -R ² (in the formula, A ² , A ³ , R ¹ and R ² are the same as above). The trifluoroalkane derivative compound according to claim 1, which is represented by: 3. A liquid crystal composition comprising the trifluoroalkane derivative compound according to claim 1 or 2.