JPH05331084A - Fluoroalkane derivative compound and liquid crystal composition containing the same - Google Patents

Abstract

PURPOSE:To provide a new fluoroalkane deriative compound having a relatively small refractive index anisotropy and a low viscosity, excellent in compatibility with other (non)liquid crystals, useful as a liquid crystal material stable to light, and permitting the low voltage driving, high duty driving, wide temperature range driving of the liquid crystals, etc. CONSTITUTION:The compound of formula I (A1 to A4 are trans-1,4-disubstituted cyclohexylene, 1,4-disubstituted phenylene; Y1, Y2 are -COO-, -OCO-, etc.; X is F, Cl; m, n are 0.1; R1, R2 are 1-10C alkyl, halogen, etc.). For example, 1,2- bis-(4-methylphenyl)-1,1,2,2-tetrafluoroethane. The compound is obtained e.g. by reacting an acetylene derivative of formula II (but not containing cyano or iodine, and Y1, Y2 are not -CidenticalC-) with iodine fluoride and further reacting the obtained compound of formula III with the iodine fluoride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluoroalkane derivative compound and a liquid crystal composition containing the compound.

[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 drive 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, when 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 a low temperature. Further, if the response speed is the same as that of the conventional one, it is possible to drive at a lower voltage or drive at a higher duty ratio, that is, high-definition drive becomes 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, RA and RB 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) R1- (A1) m-Y1-A2-CF2CX2-A3-Y2- (A4) n-R2 (1) (In the formula, A1 to A4 are independently trans-1,4-di-substituted A cyclohexylene group or a 1,4-disubstituted phenylene group, each of which is unsubstituted or may have one or more halogen or cyano group as a substituent. 1 or 2 existing in the group
One or more CH groups may be substituted with a nitrogen atom, and Y1, Y
2 are independent of each other -COO-,-OCO-,-C≡C-,-CH2CH2-,-OCH
2-,-CH2O- or a single bond, X is a fluorine atom or a chlorine atom, m, n is 0 or 1, R1 and R2
Are independently of each other an alkyl group having 1 to 10 carbon atoms, a halogen or a cyano group, and in the case of an alkyl group, oxygen is present between the carbon-carbon bond or between the carbon-carbon bond between this group and the ring. An atom may be inserted, a part of the carbon-carbon bond may be double-bonded, and one —CH 2 — group thereof may be substituted with a carbonyl group, Further, a part or all of the hydrogen atoms in the group may be substituted with a fluorine atom), and a fluoroalkane derivative compound represented by the general formula (2) R1-A2- A fluoroalkane represented by CF2CX2-A3-R2 (2) (wherein A2, A3, R1 and R2 are the same as those described above, and X is a fluorine atom or a chlorine atom). In the derivative compound and those fluoroalkane derivative compounds,
There is provided a fluoroalkane derivative compound in which X 1 is a fluorine atom, and a liquid crystal composition containing the fluoroalkane derivative compound.

The compound of the general formula (1) of the present invention has a relatively small refractive index anisotropy (Δn), has a low viscosity, and is compatible with other liquid crystals or non-liquid crystals. Excellent,
It is a chemically stable material, especially a material that is stable to light.

Specific structures of the compounds of the present invention include the following compounds. In the general formula (1), X
Is a fluorine atom or a chlorine atom. A typical compound thereof is a perfluoroalkane derivative compound in which X is a fluorine atom. Among these compounds, there are the following compounds as compounds having two rings. R1-A2-CF2CF2-A3-R2 (4)

More specifically, the compound of the general formula (4) includes the following compounds. In the following description, not only the compound represented by the general formula (4) but also “-Ph-” is 1,
Represents a 4-disubstituted phenylene group, "-Cy-" is trans-1,4
Represents a di-substituted cyclohexylene group. R1-Ph-CF2CF2-Ph-R2 (4A)

[0016]

[Chemical 2]

The following compounds are compounds in which one or two of the 1,4-di-substituted phenylene groups are substituted with a trans-1,4-di-substituted cyclohexylene group. R1-Cy-CF2CF2-Ph-R2 (4B) R1-Cy-CF2CF2-Cy-R2 (4C)

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. R1-Ph-CF2CF2-PhF-R2 (4D)

[0019]

[Chemical 3]

Further, the 1,2-di-substituted tetrafluoroethylene group of the compound represented by the general formula (4) is replaced with 1,2-di-substituted-1,1-dichloro-
There are the following compounds as compounds substituted for the 2,2-difluoroethylene group. R1-Ph-CF2CCl2-Ph-R2 (4E)

Further, as a compound having three rings, there are the following compounds. R1-A1-A2-CF2CX2-A3-R2 (5)

More specifically, the compound of the general formula (5) includes the following compounds. R1-Ph-Ph-CF2CF2-Ph-R2 (5A)

[0023]

[Chemical 4]

The following compounds are examples of compounds in which one, two or three of the 1,4-di-substituted phenylene groups are replaced with trans-1,4-di-substituted cyclohexylene groups. R1-Cy-Ph-CF2CF2-Ph-R2 (5B) R1-Ph-Cy-CF2CF2-Ph-R2 (5C) R1-Ph-Ph-CF2CF2-Cy-R2 (5D) R1-Cy-Cy-CF2CF2- Ph-R2 (5E) R1-Cy-Ph-CF2CF2-Cy-R2 (5F) R1-Ph-Cy-CF2CF2-Cy-R2 (5G) R1-Cy-Cy-CF2CF2-Cy-R2 (5H)

Further, there are the following compounds as the compound in which the 1,4-disubstituted phenylene group is a phenylene group in which some hydrogen atoms are replaced by fluorine atoms. R1-Ph-Ph-CF2CF2-PhF-R2 (5I)

In addition, the 1,2-di-substituted tetrafluoroethylene group of the compound of the general formula (5) is replaced by 1,2-di-substituted-1,1-dichloro-
There are the following compounds as compounds substituted for the 2,2-difluoroethylene group. R1-Ph-Ph-CF2CCl2-Ph-R2 (5J)

Further, there are the following compounds as compounds having four rings. R1-A1-A2-CF2CX2-A3-A4-R2 (6)

More specifically, the compound of the general formula (6) includes the following compounds. R1-Ph-Ph-CF2CF2-Ph-Ph-R2 (6A)

[0029]

[Chemical 5]

R1-Cy-Ph-CF2CF2-Ph-Ph-R2 (6B) R1-Cy-Ph-CF2CF2-Ph-Cy-R2 (6C) R1-Ph-Ph-CF2CF2-Ph-PhF-R2 (6D ) R1-Ph-Ph-CF2CCl2-Ph-Ph-R2 (6E)

In addition, in the case of a compound having three or more rings, there are the following compounds in which Y1 and Y2 between the rings are changed to other than a single bond.

R1-Ph-COO-Ph-CF2CF2-Ph-R2 (5K) R1-Ph-OCO-Ph-CF2CF2-Ph-R2 (5L) R1-Ph-C ≡C-Ph-CF2CF2-Ph-R2 (5M) R1-Ph-CH2CH2-Ph-CF2CF2-Ph-R2 (5N) R1-Ph-OCH2-Ph-CF2CF2-Ph-R2 (5O) R1-Ph-CH2O-Ph-CF2CF2-Ph-R2 (5P ) R1-Ph-COO-Ph-CF2CF2-Ph-Ph-R2 (6F) R1-Ph-OCO-Ph-CF2CF2-Ph-Ph-R2 (6G) R1-Ph-C ≡ C-Ph-CF2CF2-Ph -Ph-R2 (6H) R1-Ph-CH2CH2-Ph-CF2CF2-Ph-Ph-R2 (6I) R1-Ph-OCH2-Ph-CF2CF2-Ph-Ph-R2 (6J) R1-Ph-CH2O-Ph -CF2CF2-Ph-Ph-R2 (6K) R1-Ph-COO-Ph-CF2CF2-Ph-OCO-Ph-R2 (6L)

There are also the following compounds in which the groups A1 to A4 have a ring structure other than the 1,4-di-substituted phenylene group and the trans-1,4-di-substituted cyclohexylene group.

[0034]

[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 general 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 following formula, RC and RD are alkyl group, alkoxy group, halogen atom,
Represents a group such as a cyano group.

RC-Cy-Cy-RD RC-Cy-Ph-RD RC-Ph-Ph-RD RC-Cy-COO-Ph-RD RC-Ph-COO-Ph-RD RC-Cy-CH = CH- Ph-RD RC-Ph-CH = CH-Ph-RD RC-Cy-CH2CH2-Ph-RD RC-Ph-CH2CH2-Ph-RD RC-Ph-N = N-Ph-RD RC-Ph-NON-Ph -RD RC-Cy-COS-Ph-RD RC-Cy-Ph-Ph-RD RC-Cy-Ph-Ph-Cy-RD RC-Ph-Ph-Ph-RD RC-Cy-COO-Ph-Ph- RD RC-Cy-Ph-COO-Ph-RD RC-Cy-COO-Ph-COO-Ph-RD RC-Ph-COO-Ph-COO-Ph-RD RC-Ph-COO-Ph-OCO-Ph- RD

[0039]

[Chemical 7]

These compounds are merely examples, and the substitution of a hydrogen atom in 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
After forming an undercoat layer or color filter layer of SiO2, Al2O3, etc., providing electrodes of In2O3-SnO2 (ITO), SnO2, etc. and patterning, if necessary, an overcoat layer of polyimide, polyamide, SiO2, Al2O3, etc. Are formed, and orientation treatment is performed. Then, 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.

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

That is, an acetylene derivative compound represented by the general formula (7) (provided that it has no cyano group or iodine atom,
And Y2 is not -C≡C-) with iodine fluoride (8) to form compound (9), which is further reacted with iodine fluoride (8) to obtain a tetrafluoroethane compound (10). You can

There is also the following manufacturing method.

That is, an acetylene derivative compound of the general formula (7) (where Y1 and Y2 are not -C≡C-) is reacted with XeF2 (11) in the presence of hydrogen fluoride to give a tetrafluoroethane compound ( You can get 10).

There is also the following manufacturing method.

[0051]

Benzyl ketone compound of the general formula (12) (A1 ~
A4 is independently of each other a 1,4-disubstituted phenylene group, each of these groups being unsubstituted or substituted by 1
Or 2 or more halogen or cyano groups may be present, and 1 or 2 or more CH groups present in these groups may be substituted with a nitrogen atom, and m and n are 0. Or 1 and R1 and R2 independently of each other have 1 to 10 carbon atoms.
(Representing a perfluoroalkyl group or a perfluoroalkoxy group, a halogen or a cyano group) is reacted with chlorine gas (13) at high temperature to give a dichlorobenzyl ketone compound (14)
And Then, it is reacted with a fluorinating agent (15) such as KF or HF to obtain a difluorobenzyl ketone compound (16). Next, the carbonyl group can be chlorinated using a chlorinating agent (17) such as phosphorus pentoxide to obtain a 1,1-dichloro-2,2-difluoroethane compound (18).

Further, the tetrafluoroethane compound (20) can be obtained by reacting the compound of the general formula (16) with diethylaminosulfur trifluoride (DAST) (19).

Further, in order to introduce various groups into the compound produced by the above method and partially change the structure thereof, the following may be carried out. R1 and R2 on the side to be introduced are halogen atoms X1 and X2 other than fluorine, and m or n is 0, to the compounds of the following general formulas (21) to (23) produced by the above method, which is desired to be introduced. The group organometallic compound may be coupled in the presence of a catalyst such as Ni or Pd. Note that R1 and R2 are not halogen atoms only in the case of the following general formulas (21) to (23).

X1-A2-CF2CX2-A3- (A4) n-R2 (21) R1-A1- (A2) m-CF2CX2-A3-X2 (22) X1-A2-CF2CX2-A3-X2 (23)

R1- (A1) mM or R2- (A4) nM (M is a metal) can also be used to synthesize a 3- or 4-ring compound from a 2- or 3-ring compound. Further, in this case, in order to introduce -C≡C- into Y1 or Y2, R1- (A
1) An acetylide compound represented by mC≡CM or R2- (A4) nC≡CM (M is a metal) may be used. In addition, the general formula (2
In the case of the compound of 3), different groups can be introduced at both ends by making the halogen atoms of X1 and X2 different halogen atoms such as bromine atom and chlorine atom.

Further, in order to convert a part of the carbon-carbon bonds of R1 and R2 of the compound of the general formula (1) into a double bond, that is, to introduce an alkenyl group, the following may be carried out. R1, R2
An organometallic compound derived from an alkenyl halide may be coupled to a compound of the general formula (1) in which is a halogen atom other than fluorine in the presence of a catalyst such as Ni or Pd.

Further, the method of introducing a cyano group into R1 or R2 of the compound of the general formula (1) is carried out by using a compound of the general formula (1) in which R1 or R2 is a bromine atom or an iodine atom as Cu2 (CN) 2. All you have to do is react. Alternatively, the compound of the general formula (1) in which R1 or R2 is an alkoxycarbonyl group may be converted to a cyano group via an acid amide.

These manufacturing methods are merely examples, and various manufacturing methods can be used.

[0060]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 300 m with a gas blowing tube and a dry ice condenser
l In a three-necked flask, 12.7 g (0.05 mol) of I2 at -75 ° C,
10% F2 suspended in 200 ml of CFCl3 and diluted with N2
Iodine fluoride (IF) was produced by blowing 0.025 mol of gas over 5 hours until I2 changed from red to brown.

Bis (4-methylphenyl) acetylene 4.12
g (0.02 mol) is dissolved in 80 ml CHCl3 and cooled to -75 ° C. While stirring, 0.1 mol of IF prepared in advance was added thereto. After 5 minutes, the reaction solution was poured into 500 ml of a 5% sodium thiosulfate aqueous solution. The organic layer was separated, washed with water until neutral, and dried over MgSO4. After filtration, the solvent is distilled off,
The obtained crude product was purified by silica gel chromatography to obtain 3.50 g of 1,2-bis (4-methylphenyl) -1,1,2,2-tetrafluoroethane represented by the following formula (yield 61
%) Was obtained. CH3-Ph-CF2CF2-Ph-CH3

[0063]

[Chemical 8]

The analysis results of this compound are shown below. 19F NMR (CDCl3) δ from CFCl3 −112ppm (s) MS m / e 282 (M +) IR 1205cm-1 (C-F)

Example 2 4.12 g (0.02 mol) of bis (4-methylphenyl) acetylene was dissolved in 10 ml of CH2Cl2 in a 100 ml fluororesin reactor, and 0.42 g (0.05 mol) of XeF2 was added at room temperature, More anhydrous
0.1 g of HF was added. After stirring overnight at room temperature, 20 ml of water was added, the organic layer was separated, washed with water and dried over MgSO 4. After filtration, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to give 1,2-the same as in Example 1.
3.10 g (yield 54%) of bis (4-methylphenyl) -1,1,2,2-tetrafluoroethane was obtained. The analysis results of this compound are the same as in Example 1.

The following compounds can be synthesized in the same manner as in Example 1 by changing the starting acetylene compound. C2H5-Ph-CF2CF2-Ph-C2H5 n-C3H7-Ph-CF2CF2-Ph-C3H7 (n) (Yield 4.26 g, 63%, IR 1205cm-1 (CF), MS
M / e 338 (M +)) n-C4H9-Ph-CF2CF2-Ph-C4H9 (n) n-C5H11-Ph-CF2CF2-Ph-C5H11 (n) n-C6H13-Ph-CF2CF2-Ph-C6H13 (n ) n-C7H15-Ph-CF2CF2-Ph-C7H15 (n) n-C8H17-Ph-CF2CF2-Ph-C8H17 (n) (yield 5.93g, 62%, IR 1205cm-1 (CF), MS
M / e 478 (M +)) n-C9H19-Ph-CF2CF2-Ph-C9H19 (n) n-C10H21-Ph-CF2CF2-Ph-C10H21 (n)

CH3-Ph-CF2CF2-Ph-C5H11 (n) CH3-Ph-CF2CF2-Ph-CF3 CF3-Ph-CF2CF2-Ph-CF3 (yield 5.30 g, yield 68%, IR 1205 cm-1 (CF) , MS
M / e 390 (M +))

[0068]

[Chemical 9]

C2H5-Ph-CF2CF2-Ph-C2F5 n-C3H7-Ph-CF2CF2-Ph-C5H11 (n) CH3O-Ph-CF2CF2-Ph-CH3 C2H5O-Ph-CF2CF2-Ph-C2H5 n-C3H7O-Ph- CF2CF2-Ph-C3H7 (n) n-C4H9O-Ph-CF2CF2-Ph-C4H9 (n) n-C5H11O-Ph-CF2CF2-Ph-C5H11 (n) n-C6H13O-Ph-CF2CF2-Ph-C6H13 (n) n-C7H15O-Ph-CF2CF2-Ph-C7H15 (n) n-C8H17O-Ph-CF2CF2-Ph-C8H17 (n) n-C9H19O-Ph-CF2CF2-Ph-C9H19 (n) n-C10H21O-Ph-CF2CF2- Ph-C10H21 (n)

CH3O-Ph-CF2CF2-Ph-OCH3 (Yield 4.08 g, Yield 65%, IR 1205 cm-1 (CF), MS
M / e 314 (M +))

[0071]

[Chemical 10]

C2H5O-Ph-CF2CF2-Ph-OC2H5 n-C3H7O-Ph-CF2CF2-Ph-OC3H7 (n) n-C4H9O-Ph-CF2CF2-Ph-OC4H9 (n) n-C5H11O-Ph-CF2CF2-Ph- OC5H11 (n) n-C6H13O-Ph-CF2CF2-Ph-OC6H13 (n) n-C7H15O-Ph-CF2CF2-Ph-OC7H15 (n) n-C8H17O-Ph-CF2CF2-Ph-OC8H17 (n) n-C9H19O- Ph-CF2CF2-Ph-OC9H19 (n) n-C10H21O-Ph-CF2CF2-Ph-OC10H21 (n)

Example 3 5.98 g (0.02 mol) of 1- (4-bromophenyl) -2- (4-n-propylphenyl) acetylene was used instead of the bis (4-methylphenyl) acetylene used in Example 1. ) The reaction was performed in the same manner as in Example 1 except that 1- (4-bromophenyl)-was used.
4.50 g (yield 60%) of 2- (4-n-propylphenyl) -1,1,2,2-tetrafluoroethane was obtained. n-C3H7-Ph-CF2CF2-Ph-Br

Next, 1.08 g (0.012 mol) of CuCN was added to anhydrous DMCN.
Dissolve by heating to 90 ° C in 10 ml of SO. Then, under stirring, the obtained 1- (4-bromophenyl) -2- (4-n-propylphenyl) -1,1,2,2-tetrafluoroethane 4.50 g (0.012
(mol) DMSO solution is added dropwise. Then at 150 ℃ 1
After stirring for an hour, cool to room temperature. 50 ml of water was poured, the mixture was extracted with methylene chloride, the organic layer was washed with saturated saline, and CaCl2 was added.
To dry. After filtration, the solvent was evaporated, the obtained solid was purified by silica gel column chromatography, and 1- (4-
Cyanophenyl) -2- (4-n-propylphenyl) -1,1,2,2-
3.47 g (yield 90%) of tetrafluoroethane was obtained. n-C3H7-Ph-CF2-CF2-Ph-CN

[0075]

[Chemical 11]

The analysis results of this compound are shown below. MS m / e 321 (M +) IR 2260cm-1 (C≡N), 1205cm-1 (C-F)

The following compounds can be similarly synthesized. CH3-Ph-CF2CF2-Ph-CN C2H5-Ph-CF2CF2-Ph-CN n-C5H11-Ph-CF2CF2-Ph-CN n-C7H15-Ph-CF2CF2-Ph-CN n-C10H21-Ph-CF2CF2-Ph- CN CH3O-Ph-CF2CF2-Ph-CN n-C3H7O-Ph-CF2CF2-Ph-CN n-C5H11O-Ph-CF2CF2-Ph-CN n-C7H15O-Ph-CF2CF2-Ph-CN n-C10H21O-Ph-CF2CF2 -Ph-CN

Example 4 Instead of the bis (4-methylphenyl) acetylene used in Example 1, bis (4-chlorophenyl) acetylene was added to 4.9%.
The reaction was performed in the same manner as in Example 1 except that 4 g (0.02 mol) was used to obtain 4.13 g (yield 64%) of 1,2-bis (4-chlorophenyl) -1,1,2,2-tetrafluoroethane. It was Cl-Ph-CF2CF2-Ph-Cl

[0079]

[Chemical formula 12]

The analysis results of this compound are shown below. 19F NMR (CDCl3) δ from CFCl3 −112ppm (s) MS m / e 321 (M +) IR 1205cm-1 (C-F)

The following compounds can be similarly synthesized. C3H7-Ph-CF2CF2-Ph-Cl n-C5H11-Ph-CF2CF2-Ph-Cl n-C10H21-Ph-CF2CF2-Ph-Cl CH3O-Ph-CF2CF2-Ph-Cl n-C3H7O-Ph-CF2CF2-Ph- Cl n-C5H11O-Ph-CF2CF2-Ph-Cl n-C10H21O-Ph-CF2CF2-Ph-Cl

Example 5 In place of the bis (4-methylphenyl) acetylene of Example 1, 3.36 g (0.02 mol) of tolan was used to carry out the same reaction to obtain 1,2-diphenyl-1,1,2, 2-tetrafluoroethane
3.43 g (yield 68%) was obtained.

In a 100 ml three-necked flask equipped with a reflux tube, AlCl
3 Charge 7.25g (0.054mol) and 20ml of methylene chloride, 0 ℃
After cooling to 4, acetyl chloride 4.27 g (0.054 mol) was added dropwise, and the mixture was stirred for 1 hour. Then, at 0 ° C., a methylene chloride solution containing 3.43 g of the obtained 1,2-diphenyl-1,1,2,2-tetrafluoroethane was added dropwise. After returning to room temperature, the mixture was stirred for 2 hours and poured into 100 g of ice. The organic layer was separated, dried and evaporated to remove the solvent, and the resulting solid was purified by silica gel column chromatography to give 1,2-bis (4-acetylphenyl) -1,1,2,2. -3.43 g of tetrafluoroethane (yield 75
%)Obtained. CH3CO-Ph-CF2CF2-Ph-COCH3

[0084]

[Chemical 13]

The analysis results of this compound are shown below. MS m / e 338 (M +) IR 1205cm-1 (C-F)

The following compounds can be similarly synthesized. C2H5CO-Ph-CF2CF2-Ph-COC2H5 n-C4H9CO-Ph-CF2CF2-Ph-COC4H9 (n) n-C9H19CO-Ph-CF2CF2-Ph-COC9H19 (n)

Example 6 In a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere.
0.96 g of Mg (0.04 mol) and 10 ml of dry THF are added, and a few drops of 1-bromopropane are added thereto. Then vinyl bromide 3.
85 g (0.036 mol) are added dropwise at such a rate that the exotherm continues. After the addition is complete, continue refluxing for another hour and allow to cool to room temperature.

This solution was separately prepared under argon atmosphere in a 100 ml three-necked flask equipped with a reflux tube, 1- (4-bromophenyl) -2- (4-n-propylphenyl) -1,1,2, 2-Tetrafluoroethane 4.50 g (0.012 mol) and 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl2
(dppp)] 1.26 g in dry THF solution 20 ml is added dropwise using a dropping funnel. After dropping, the mixture was refluxed for 6 hours, cooled to room temperature, and added with 20 ml of water. 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 3.01 g of 1- (4-vinylphenyl) -2- (4-propylphenyl) -1,1,2,2-tetrafluoroethane (yield: Rate 78%). n-C3H7-Ph-CF2CF2-Ph-CH = CH2

[0089]

[Chemical 14]

The analysis results of this compound are shown below. MS m / e 322 (M +) IR 1205cm-1 (C-F)

The following compounds can be similarly synthesized. CH3-Ph-CF2CF2-Ph-CH = CH2 n-C5H11-Ph-CF2CF2-Ph-CH = CH2 n-C10H21-Ph-CF2CF2-Ph-CH = CH2

Example 7 Instead of the bis (4-methylphenyl) acetylene used in Example 1, 1- (4-methylphenyl) -2- (trans-4-
Methylcyclohexyl) 4.24 g (0.02 mol) of acetylene
The reaction was carried out in the same manner as in Example 1 except that the 1- (4-methylphenyl) -2- (trans-4-methylcyclohexyl)-was used.
3.80 g (yield 66%) of 1,1,2,2-tetrafluoroethane was obtained. CH3-Ph-CF2CF2-Cy-CH3

[0093]

[Chemical 15]

The analysis results of this compound are shown below. MS m / e 288 (M +) IR 1205cm-1 (C-F)

The following compounds can be similarly synthesized. n-C3H7-Ph-CF2CF2-Cy-C3H7 (n) n-C5H11-Ph-CF2CF2-Cy-C5H11 (n) CH3O-Ph-CF2CF2-Cy-CH3 n-C5H11O-Ph-CF2CF2-Cy-C5H11 (n ) CH3O-Ph-CF2CF2-Cy-OCH3 n-C5H11O-Ph-CF2CF2-Cy-OC5H11 (n)

CH3-Cy-CF2CF2-Cy-CH3 n-C3H7-Cy-CF2CF2-Cy-C3H7 (n) n-C5H11-Cy-CF2CF2-Cy-C5H11 (n) CH3O-Cy-CF2CF2-Cy-CH3 n -C5H11O-Cy-CF2CF2-Cy-C5H11 (n) CH3O-Cy-CF2CF2-Cy-OCH3 n-C5H11O-Cy-CF2CF2-Cy-OC5H11 (n)

In the following example, PhF is fluorine-substituted-1,4
Represents a di-substituted phenylene group. CH3-PhF-CF2CF2-PhF-CH3 (Yield 4.07g, Yield 64%, IR 1205cm-1 (CF), MS
M / e 318 (M +))

[0098]

[Chemical 16]

N-C3H7-PhF-CF2CF2-PhF-C3H7 (n) n-C5H11-PhF-CF2CF2-PhF-C5H11 (n) CH3-Ph-CF2CF2-PhF-CH3 n-C3H7-Ph-CF2CF2-PhF- C3H7 (n) n-C5H11-Ph-CF2CF2-PhF-C5H11 (n) CH3O-Ph-CF2CF2-PhF-CH3 n-C5H11O-Ph-CF2CF2-PhF-C5H11 (n) CH3O-Ph-CF2CF2-PhF-OCH3 n-C5H11O-Ph-CF2CF2-PhF-OC5H11 (n) CH3-Cy-CF2CF2-PhF-CH3

Example 8 In a 100 ml glass three-necked flask equipped with a reflux tube and a gas injection tube, 26.5 g (0.1%) of 4,4'-dichlorobenzyl phenyl ketone was added.
mol) was charged and heated to 150 ° C. 71g of Cl2 gas here
, While keeping the reaction temperature at 150 to 170 ° C, it was blown in over 3 hours. After cooling, add 50 ml of methylene chloride, wash with water, separate the organic layer, dry and evaporate the solvent to remove α, α,
31.7 g of 4,4'-tetrachlorobenzyl phenyl ketone was obtained.

In a 100 ml glass three-necked flask equipped with a reflux tube, 31.7 g of the obtained α, α, 4,4'-tetrachlorobenzylphenyl ketone and 1 ml of spray-dried potassium fluoride were added.
3.2 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 4,4′-dichloro-α,
19.6 g of α-difluorobenzyl phenyl ketone (yield
65%) obtained. Cl-Ph-CF2CO-Ph-Cl

A 100 ml glass three-necked flask equipped with a reflux tube was charged with 19.6 g of the obtained 4,4′-dichloro-α, α-difluorobenzylphenyl ketone and 67.8 g of phosphorus pentachloride, and the mixture was reacted at 130 ° C. for 5 hours. Let After cooling, 50 g of methylene chloride was added and poured into 200 g of ice. The organic layer was separated, dried and the solvent was distilled off to obtain 22.0 g of 1,2-bis (4-chlorophenyl) -1,1-dichloro-2,2-difluoroethane. Cl-Ph-CF2CCl2-Ph-Cl

Under argon atmosphere, into a 100 ml three-necked flask equipped with a reflux tube, 9.91 g (0.41 mol) of Mg and 20 ml of dry THF were placed, and a few drops of 1-bromopropane were added thereto. Then 1-
Bromopropane 22.8 g (0.185 mol) is added dropwise at a rate of continued exotherm. After the dropping is completed, the mixture is refluxed for another hour and then left to cool to room temperature. This solution was separately prepared under argon atmosphere in a 100 ml three-necked flask equipped with a reflux tube 1,2-.
Bis (4-chlorophenyl) -1,1-dichloro-2,2-difluoroethane 22.0 g (0.0618 mol) and 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl2 (dppp)
] Using a dropping funnel, add dropwise to 20 ml of dry THF solution containing 1.3 g.

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 give 17.0 g of 1,2-bis (4-n-propylphenyl) -1,1-dichloro-2,2-difluoroethane (yield 74%). Obtained. n-C3H7-Ph-CF2CCl2-Ph-C3H7 (n)

[0105]

[Chemical 17]

The analysis results of this compound are shown below. MS m / e 371 (M +) IR 1205cm-1 (C-F)

The following compounds can be similarly synthesized. CH3-Ph-CF2CCl2-Ph-CH3 n-C5H11-Ph-CF2CCl2-Ph-C5H11 (n)

Example 9 In place of the bis (4-methylphenyl) acetylene used in Example 1, 5.76 g (0.02 mol) of 4-methyl-4 ′-(trans-4-methylcyclohexyl) tran was used, except that Reaction was carried out in the same manner as in Example 1, and 1- (4-methylphenyl) -2- [4
-(Trans-4-methylcyclohexyl) phenyl] -1,1,
4.59 g (yield 63%) of 2,2-tetrafluoroethane was obtained. CH3-Cy-Ph-CF2CF2-Ph-CH3

[0109]

[Chemical 18]

The analysis results of this compound are shown below. MS m / e 364 (M +) IR 1205cm-1 (C-F)

Example 10 Same as Example 8 except that 24.9 g (0.1 mol) of 4-chlorobenzyl-4-fluorophenylketone was used instead of 4,4′-dichlorobenzylphenylketone used in Example 8. 4-chloro-α, α-difluorobenzyl-4
-19.9 g (yield 70%) of fluorophenyl ketone was obtained. Cl-Ph-CF2CO-Ph-F

Next, 19.9 g of the obtained 4-chloro-α, α-difluorobenzyl-4-fluorophenyl ketone was dissolved in 100 ml of dry methylene chloride, and DAST was added in an amount of 22.6 g (0.14 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 evaporated and the resulting crude crystals were purified by silica gel column chromatography to give 1- (4-chlorophenyl) -2- (4-fluorophenyl) -1,1,2,2. -18.7 g of tetrafluoroethane (yield 87
%)Obtained. Cl-Ph-CF2CF2-Ph-F

Then, the obtained 1- (4-chlorophenyl)-
2- (4-Fluorophenyl) -1,1,2,2-tetrafluoroethane (18.7 g) was dissolved in dry DMF (100 ml), and sodium ethoxide (10.4 g, 0.15 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 resulting crude crystals were purified by silica gel column chromatography to give 1- (4-chlorophenyl)-.
12.1 g (yield 60%) of 2- (4-ethoxyphenyl) -1,1,2,2-tetrafluoroethane was obtained. Cl-Ph-CF2CF2-Ph-OC2H5

Then, in an argon atmosphere, with a reflux pipe
In a 300 ml three-necked flask, Mg 2.23 g (0.068 mol) and dry TH
F 100 ml was added. Then add a few drops of 1-bromopropane, and add 18.9g of 4-n-propylcyclohexyl bromide.
(0.065 mol) was added dropwise at such a rate that exotherm continued. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.
Separately, add this solution to a 300 m
l In a three-necked flask, the obtained 1- (4-chlorophenyl) -2- (4-ethoxyphenyl) -1,1,2,2-tetrafluoroethane 7.23 g (0.022 mol) and NiCl2 (dppp) 1.5 50 ml of a dry THF solution containing g was prepared and added dropwise thereto using a dropping funnel.

After the dropping, the mixture was further stirred at room temperature for 24 hours,
Poured into 300 ml of water. Further, 200 ml of 20% hydrochloric acid was added to separate the organic layer, which was washed with water and dried, and then the solvent was distilled off. The resulting crude product was purified by silica gel column chromatography to give 1- [4- (4-n-propylcyclohexyl) phenyl] -2- (4-ethoxyphenyl) -1,1,2,2-tetra 2.75 g (yield 30%) of fluoroethane was obtained. n-C3H7-Cy-Ph-CF2CF2-Ph-OC2H5

[0116]

[Chemical 19]

The analysis results of this compound are shown below. 19F NMR (CDCl3) δppm from CFCl3 -110.2 (t), -110.8 (t) MS m / e 422 (M +) IR 1205cm-1 (C-F) Melting point (Tm) 63.1 ° C

The following compounds are synthesized in the same manner as in Example 9 or Example 10. n-C3H7-Cy-Ph-CF2CF2-Ph-C3H7 (n) n-C5H11-Cy-Ph-CF2CF2-Ph-C5H11 (n) CH3O-Cy-Ph-CF2CF2-Ph-CH3 n-C5H11O-Cy-Ph -CF2CF2-Ph-C5H11 (n) CH3O-Cy-Ph-CF2CF2-Ph-OCH3 n-C5H11O-Cy-Ph-CF2CF2-Ph-OC5H11 (n) CH3-Cy-Ph-CF2CF2-PhF-CH3

CH3-Ph-Ph-CF2CF2-Ph-CH3 n-C3H7-Ph-Ph-CF2CF2-Ph-C3H7 (n) n-C5H11-Ph-Ph-CF2CF2-Ph-C5H11 (n) CH3O-Ph- Ph-CF2CF2-Ph-CH3 n-C5H11O-Ph-Ph-CF2CF2-Ph-C5H11 (n) CH3O-Ph-Ph-CF2CF2-Ph-OCH3 n-C5H11O-Ph-Ph-CF2CF2-Ph-OC5H11 (n) CH3-Ph-Ph-CF2CF2-PhF-CH3

CH3-Cy-Cy-CF2CF2-Ph-CH3 n-C5H11-Cy-Cy-CF2CF2-Ph-C5H11 (n) n-C3H7-Cy-Cy-CF2CF2-Ph-C3H7 (n) CH3O-Cy- Cy-CF2CF2-Ph-CH3 n-C5H11O-Cy-Cy-CF2CF2-Ph-C5H11 (n) CH3O-Cy-Cy-CF2CF2-Ph-OCH3 n-C5H11O-Cy-Cy-CF2CF2-Ph-OC5H11 (n) CH3-Cy-Cy-CF2CF2-PhF-CH3

CH3-Ph-Cy-CF2CF2-Ph-CH3 n-C5H11-Ph-Cy-CF2CF2-Ph-C5H11 (n) n-C3H7-Ph-Cy-CF2CF2-Ph-C3H7 (n) CH3O-Ph- Cy-CF2CF2-Ph-CH3 n-C5H11O-Ph-Cy-CF2CF2-Ph-C5H11 (n) CH3O-Ph-Cy-CF2CF2-Ph-OCH3 n-C5H11O-Ph-Cy-CF2CF2-Ph-OC5H11 (n) CH3-Ph-Cy-CF2CF2-PhF-CH3

CH3-Cy-Cy-CF2CF2-Cy-CH3 n-C5H11-Cy-Cy-CF2CF2-Cy-C5H11 (n) n-C3H7-Cy-Cy-CF2CF2-Cy-C3H7 (n) CH3O-Cy- Cy-CF2CF2-Cy-CH3 n-C5H11O-Cy-Cy-CF2CF2-Cy-C5H11 (n) CH3O-Cy-Cy-CF2CF2-Cy-OCH3 n-C5H11O-Cy-Cy-CF2CF2-Cy-OC5H11 (n)

Further, the following compounds can be prepared by utilizing the techniques of Examples 2 and 3. CH3-Cy-Ph-CF2CF2-Ph-Cl CH3-Cy-Ph-CF2CF2-Ph-CN CH3-Ph-Ph-CF2CF2-Ph-Cl CH3-Ph-Ph-CF2CF2-Ph-CN

Example 11 In place of the bis (4-methylphenyl) acetylene used in Example 1, 7.40 g (0.02 mol) of 1,2-bis [4- (trans-4-methylcyclohexyl)] tran was used. Other than that, the reaction was performed in the same manner as in Example 1 to obtain 5.44 g of 1,2-bis [4- (trans-4-methylcyclohexyl) phenyl) -1,1,2,2-tetrafluoroethane (yield 61% )Obtained. CH3-Cy-Ph-CF2CF2-Ph-Cy-CH3

[0125]

[Chemical 20]

The analysis results of this compound are shown below. MS m / e 446 (M +) IR 1205cm-1 (C-F)

Similarly, the following compounds are synthesized. n-C3H7-Cy-Ph-CF2CF2-Ph-Cy-C3H7 (n) n-C5H11-Cy-Ph-CF2CF2-Ph-Cy-C5H11 (n) CH3O-Cy-Ph-CF2CF2-Ph-Cy-CH3 n -C5H11O-Cy-Ph-CF2CF2-Ph-Cy-C5H11 (n) CH3O-Cy-Ph-CF2CF2-Ph-Cy-OCH3 n-C5H11O-Cy-Ph-CF2CF2-Ph-Cy-OC5H11 (n)

CH3-Ph-Ph-CF2CF2-Ph-Ph-CH3 n-C3H7-Ph-Ph-CF2CF2-Ph-Ph-C3H7 (n) n-C5H11-Ph-Ph-CF2CF2-Ph-Ph-C5H11 ( n) CH3O-Ph-Ph-CF2CF2-Ph-Ph-CH3 n-C5H11O-Ph-Ph-CF2CF2-Ph-Ph-C5H11 (n) CH3O-Ph-Ph-CF2CF2-Ph-Ph-OCH3 n-C5H11O- Ph-Ph-CF2CF2-Ph-Ph-OC5H11 (n) CH3-Ph-Ph-CF2CF2-Ph-PhF-CH3

CH3-Cy-Ph-CF2CF2-Ph-Ph-CH3 CH3O-Cy-Ph-CF2CF2-Ph-Ph-CH3 CH3-Cy-Cy-CF2CF2-Ph-Ph-CH3 CH3O-Cy-Cy-CF2CF2- Ph-Ph-CH3

Further, the following compounds can be produced by utilizing the techniques of Examples 2 and 3. Cl-Cy-Ph-CF2CF2-Ph-Cy-Cl CH3-Cy-Ph-CF2CF2-Ph-Cy-Cl CH3-Cy-Ph-CF2CF2-Ph-Cy-CN Cl-Ph-Ph-CF2CF2-Ph-Ph -Cl CH3-Ph-Ph-CF2CF2-Ph-Ph-Cl CH3-Ph-Ph-CF2CF2-Ph-Ph-CN

Example 12 In place of the bis (4-methylphenyl) acetylene used in Example 1, 1.16 g (0.02 mol) of 1- (4-hydroxyphenyl) -2- (4-methylphenyl) acetylene was used. Other than that, the reaction was performed in the same manner as in Example 1 to obtain 3.81 g of 1- (4-hydroxyphenyl) -2- (4-methylphenyl) -1,1,2,2-tetrafluoroethane (yield 67%). Obtained.

3.81 g of 1- (4-hydroxyphenyl) -2- (4-methylphenyl) -1,1,2,2-tetrafluoroethane obtained in a 100 ml glass reactor was then added to 10 ml of CH2C
Dissolve in l2, add 1.59 g (0.05 mol) of pyridine at room temperature,
After cooling to 0 ° C, 3.11 g of p-toluyl chloride was further added dropwise. After stirring at room temperature for 1 hour, cooling, diluted hydrochloric acid was added, the solvent was distilled off after filtration, and the crude crystals obtained were purified by silica gel column chromatography to give 1- [4- (4-methylbenzoyl). 5.71 g of (oxy) phenyl] -2- (4-methylphenyl) -1,1,2,2-tetrafluoroethane (yield 94
%)Obtained. CH3-Ph-COO-Ph-CF2CF2-Ph-CH3

[0133]

[Chemical 21]

The analysis results of this compound are shown below. MS m / e 402 (M +) IR 1205cm-1 (C-F)

Similarly, the following compounds can be synthesized. n-C3H7-Ph-COO-Ph-CF2CF2-Ph-C3H7 (n) CH3-Ph-COO-Ph-CF2CF2-Cy-CH3 CH3-Ph-COO-Ph-CF2CF2-Ph-COO-Ph-CH3

Example 13 1-obtained in Example 11 in a 100 ml glass reactor
(4-hydroxyphenyl) -2- (4-methylphenyl) -1,1,
3.82 g (0.0134 mol) of 2,2-tetrafluoroethane, 2.04 g of potassium carbonate and 20 ml of acetone were added, and further, 2.48 g of α-bromo-p-xylene was added dropwise at room temperature. Then, the mixture was refluxed for 4 hours, cooled, filtered, and the solvent was distilled off. The obtained crude crystals were purified by silica gel column chromatography to give 1- [4- (4-methylbenzyloxy) phenyl]- 5.04 g (yield 97%) of 2- (4-methylphenyl) -1,1,2,2-tetrafluoroethane was obtained. CH3-Ph-CH2O-Ph-CF2CF2-Ph-CH3

[0137]

[Chemical formula 22]

The analytical results of this compound are shown below. MS m / e 388 (M +) IR 1205cm-1 (C-F)

Similarly, the following compounds can be synthesized. n-C3H7-Ph-CH2O-Ph-CF2CF2-Ph-C3H7 (n) CH3-Ph-CH2O-Ph-CF2CF2-Cy-CH3 CH3-Ph-CH2O-Ph-CF2CF2-Ph-OCH2-Ph-CH3

Example 14 In a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere.
Add 0.96g Mg (0.04mol) and 20ml dry THF and put 1-
A few drops of bromopropane were added. Then 2- (p-toluyl)
7.09 g (0.036 mol) of vinyl bromide was added dropwise at such a rate that heat generation continued. After the dropping was completed, the reflux was continued for another hour,
It was left to cool to room temperature. This solution was separately added to a 1- (4-bromophenyl) -2- (4-n-propylphenyl) -1,1 obtained in Example 3 in a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere. 4.50 g (0.012mo) of 2,2,2-tetrafluoroethane
l) and 20 g of dry THF solution containing 0.2 g of NiCl2 (dppp) were added 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 was added to separate the organic layer, which was washed with water and dried, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to give 1- [4- (p-methylstinyl) phenyl] -2- (4-n-
Propylphenyl) -1,1,2,2-tetrafluoroethane 3.
56 g (yield 72%) was obtained. CH3-Ph-CH = CH-Ph-CF2CF2-Ph-C3H7 (n)

[0142]

[Chemical formula 23]

The analysis results of this compound are shown below. MS m / e 412 (M +) IR 1205cm-1 (C-F)

Similarly, the following compounds can be synthesized. n-C3H7-Ph-CH = CH-Ph-CF2CF2-Ph-C3H7 (n) CH3-Ph-CH = CH-Ph-CF2CF2-Cy-CH3 CH3-Ph-CH = CH-Ph-CF2CF2-Ph-CH = CH-Ph-CH3

Example 15 Instead of the bis (4-methylphenyl) acetylene used in Example 1, 6.92 g (0.02 g) of 1- (4-iodophenyl) -2- (4-n-propylphenyl) acetylene was used. mol) was used and the reaction was carried out in the same manner as in Example 1 to obtain 1- (4-iodophenyl)-
5.06 g (yield 60%) of 2- (4-n-propylphenyl) -1,1,2,2-tetrafluoroethane was obtained. I-Ph-CF2CF2-Ph-C3H7 (n)

Under an argon atmosphere, 2.86 g of cuprous iodide and 1- (4-iodophenyl) -2- (4-n were placed in a 100 ml three-necked flask.
-Propylphenyl) -1,1,2,2-tetrafluoroethane 5.
06 g and 30 ml of anhydrous THF were charged and stirred at room temperature. Add 1.42 g of n-butylamine and 1.5 of p-toluylacetylene.
3 g was added. Then, anhydrous THF containing 0.69 g of (Ph3P) 4Pd
10 ml of the solution was added, and the mixture was stirred at room temperature for 2 hours. Saturated NaHCO3
After adding 30 ml of water and separating the layers, the mixture was extracted with methylene chloride. After the solvent was distilled off, the residue was purified by silica gel column chromatography and purified by 1- (4-n-propylphenyl) -2- [4- (2-p-toluylethynyl) phenyl] -1,1,2,2-tetrafluoro. Ethane 3.
44 g (yield 70%) was obtained. CH3-Ph-C≡C-Ph-CF2CF2-Ph-C3H7 (n)

[0147]

[Chemical formula 24]

The analysis results of this compound are shown below. MS m / e 410 (M +) IR 1205cm-1 (C-F)

Similarly, the following compounds can be synthesized. n-C3H7-Ph-C ≡C-Ph-CF2CF2-Ph-C3H7 (n) CH3-Ph-C ≡C-Ph-CF2CF2-Cy-CH3 CH3-Ph-C ≡C-Ph-CF2CF2-Ph-C ≡ C-Ph-CH3

Example 16 In place of the bis (4-methylphenyl) acetylene used in Example 1, 1.16 g (0.02 mol) of 1- (4-methylphenyl) -2- (5-methylpyrimidinyl) acetylene is used. Other than that, the reaction was performed in the same manner as in Example 1, and 1- (4-methylphenyl)-
2.69 g (yield 65%) of 2- (5-methylpyrimidinyl) -1,1,2,2-tetrafluoroethane was obtained.

[0151]

[Chemical 25]

The analysis results of this compound are shown below. MS m / e 284 (M +) IR 1205 cm-1 (C-F) Similarly, the following compounds can be synthesized.

[0153]

[Chemical formula 26]

Example 17 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.

Also, a liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Inc.
Has a clearing point (Tc) of 85.9 ° C. and a refractive index anisotropy (Δn) of 0.125. 5 wt% of the compound of Example 10 of the present invention was added to 95 wt% of this liquid crystal composition to obtain a liquid crystal composition. This composition has a clearing point (Tc) of 84.3 ° C. and a refractive index anisotropy (Δn) of 0.122, which is a conventional example (only the liquid crystal composition “ZLI-1565” manufactured by Merck).
And the viscosity decreased. 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.

[0156]

The general formula (1) R1- (A1) m-Y1-A2-CF2CX2-A3-Y2- (A4) n-R2 (1) (A1 to A4, R1, R2, Y1, The compounds represented by Y2, X, m, and n have the above-mentioned meanings) have a low viscosity, and when used as a liquid crystal composition, the response speed is improved even when added in a small amount. High duty drive and wide temperature range operation are 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 number Office reference number FI Technical indication location C07C 69/76 A 9279-4H Z 9279-4H 69/773 9279-4H 69/92 9279-4H 69 / 94 9279-4H C07D 211/14 9165-4C 211/38 9165-4C 211/62 9165-4C 239/26 8615-4C 319/06 C09K 19/14 7457-4H 19/16 7457-4H 19/18 7457 −4H 19/20 7457-4H 19/30 7457-4H 19/34 7457-4H (72) Inventor Takashi Miyajima 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Takahide Taka Sho 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture AZ Technology Co., Ltd. (72) Inventor Satoru Machida 4-16-31 Okada, Samukawa-cho, Takaza-gun, Kanagawa Prefecture

Claims (4)

[Claims] 1. General formula (1) R1- (A1) m-Y1-A2-CF2CX2-A3-Y2- (A4) n-R2 (1) (In the formula, A1 to A4 are independent of each other. -1,4-disubstituted cyclohexylene group or 1,4-disubstituted phenylene group, each of which is unsubstituted or has one or more halogen or cyano group as a substituent Optionally, one or two present in these groups
One or more CH groups may be substituted with a nitrogen atom, and Y1, Y
2 are independent of each other -COO-,-OCO-,-C≡C-,-CH2CH2-,-OCH
2-,-CH2O- or a single bond, X is a fluorine atom or a chlorine atom, m, n is 0 or 1, R1 and R2
Are independently of each other an alkyl group having 1 to 10 carbon atoms, a halogen or a cyano group, and in the case of an alkyl group, oxygen is present between the carbon-carbon bond or between the carbon-carbon bond between this group and the ring. An atom may be inserted, a part of the carbon-carbon bond may be double-bonded, and one —CH 2 — group thereof may be substituted with a carbonyl group, In addition, a part or all of the hydrogen atoms in the group may be substituted with a fluorine atom), a fluoroalkane derivative compound. 2. General formula (2) R1-A2-CF2CX2-A3-R2 (2) (In the formula, A2, A3, R1 and R2 are the same as those described above, and X is a fluorine atom or a chlorine atom. Is represented). The fluoroalkane derivative compound according to claim 1, wherein 3. The fluoroalkane derivative compound according to claim 1 or 2, wherein X is a fluorine atom. 4. A liquid crystal composition containing the fluoroalkane derivative compound according to claim 1.