JP3122199B2 - Liquid crystal composition and liquid crystal display device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to a liquid crystal display device using a liquid crystal composition Oyo Bisore containing difluoromethylene compounds.

[0002]

2. Description of the Related Art Liquid crystal display devices include watches, calculators,
In recent years, measuring instruments, automotive instruments, copiers, cameras, OA
It has begun to be used in various applications such as display devices for equipment and display devices for home appliances, and various performance requirements such as a wide operating temperature range, low operating voltage, high-speed response, high contrast ratio, wide viewing angle, and chemical stability. Has been made.

However, at present, no material satisfying all of these properties in a single material, is in a state that meets the required performance as a liquid crystal composition by mixing a plurality of liquid crystal and non-crystal material . Therefore, not all of the various properties, one or also liquid crystal excellent in two or more properties of the material development of non-liquid crystal is desired.

[0004]

In the field of display devices using liquid crystals, it is desired to improve the performance of the display devices, such as low-voltage driving, high-definition display, high contrast ratio, wide viewing angle characteristics, low-temperature response characteristics, and wide operation. A temperature range or the like is desired, and if any of them is improved, there is a tendency that one of them is sacrificed. For this reason, liquid crystal compounds and non-liquid crystal compounds having different characteristics are mixed to form a composition so as to obtain desired characteristics.

In particular, a liquid crystal composition having a large dielectric anisotropy (.DELTA..epsilon.) Is desired for performing time-division driving.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a novel liquid crystal composition for solving the above-mentioned problems, and has a general formula (1) R ^1- (A ¹ ) _m -Y ¹ -A ² -Z-CF ₂ -A ³ -Y ^2- (A ⁴ ) _n -R ² (a) R ^1- (A ¹ ) _m -Y ¹ -is an electron-withdrawing group, and (b) R ^{2 _{- (a 4) n -Y 2}} - is an electron donating ^{group, (c) a 1, a} 3, a 4 is trans independently of one another - 1,4 - cyclo <br/> hexylene or 1,4 - a full Eniren group, a ² is 1,4 -
A full Eniren group, A ^1, A ² is one or two or more halogen atoms as a substituent, may have a cyano group, A ^3, one present in the group A ⁴ or 2 More than CH
The group may be substituted by a nitrogen atom, (d) Y ¹ is -OCO-, -CO- or a single bond, and (e) Y ² is -C≡C-, -CH = CH-,- CH ₂ CH _2- , -OCH _2- , -CH ₂ O-
Or (f) Z is an oxygen atom or a sulfur atom, (g) m and n are independently 0 or 1, and (h) R ¹ is one or more hydrogen atoms. An alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, an alkoxy group,
Acyl group or alkoxycarbonyl group, halogen source
A child or a cyano group, the carbon - may also be part of the carbon bond is a double bond, also carbon - may be an oxygen atom is inserted between carbon bonds, (i) R ² is An alkyl group or an alkoxy group having 1 to 10 carbon atoms, a part of the carbon-carbon bond may be a double bond, or an oxygen atom may be inserted between the carbon-carbon bond. It is intended to provide a liquid crystal composition characterized by containing a difluoromethylene compound represented by the following formula:

[0007] or R ¹ of that is an acyl group or an alkoxycarbonyl group, or difluoromethylene compounds Y ¹ is -CO-, or, R ¹ is substituted with one or more of its hydrogen atoms by fluorine atoms carbon A liquid crystal composition characterized by containing a difluoromethylene compound which is an alkyl group or an alkoxy group having a number of 1 to 10, a halogen atom or a cyano group is preferable .

The general formula (1) R ^1- (A ¹ ) _m -Y ¹ -A ² -Z-CF ₂ -A ³ -Y ^2- (A ⁴ ) _n -R ² ( b ) R ^2- (a ⁴⁾ _n -Y ² - is an electron donating ^{group, (c ') a 1,} a 3, a 4 is trans independently of one another 1,4 - shea click <br/> Rohekishiren group or 1,4 - a full Eniren group, a ² is 1,4 has one or two or more halogen atoms or a cyano group as a substituent - an off Eniren group, a ¹ is a substituent It may have one or more halogen atoms or cyano groups, and one or more CH groups present in the groups A ³ and A ⁴ may be substituted with nitrogen atoms. , (d) Y ¹ is -OCO-, is -CO- or a single bond, (e) Y ² is -C≡C -, - CH = CH-, -CH 2 CH 2 -, - OCH 2 -, -CH ₂ O-
Or ( f ) Z is an oxygen atom or a sulfur atom, ( g ) m and n are each independently 0 or 1, and ( h ) R ¹ is one or more hydrogen atoms. An alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, an alkoxy group,
Acyl group or alkoxycarbonyl group, halogen source
A child or a cyano group, the carbon - may also be part of the carbon bond is a double bond, also carbon - may be an oxygen atom is inserted between carbon bonds, (i) R ² is An alkyl group or an alkoxy group having 1 to 10 carbon atoms, a part of the carbon-carbon bond may be a double bond, or an oxygen atom may be inserted between the carbon-carbon bond. It is intended to provide a liquid crystal composition characterized by containing a difluoromethylene compound represented by the following formula:

Further , Y ¹ is —CO—, and A ² and A ^{3 are} both
The above liquid crystal, which is a 1,4-phenylene group having no substituent
It provides a composition. Another object of the present invention is to provide a liquid crystal display device characterized in that the above liquid crystal composition is sandwiched between a pair of substrates with electrodes and a voltage is applied to drive the substrate in a time division manner.

[0010] Compounds of general formula (1) used in the present invention has a large dielectric anisotropy ([Delta] [epsilon]), and, or other liquid crystal excellent in compatibility with non-liquid crystalline, chemically Is a stable and stable material, the dielectric anisotropy of the mixed liquid crystal composition can be increased.

The compound used in the liquid crystal composition of the present invention is a compound having an asymmetric structure. General formula (1) is converted to Q ¹ -A ² -Z-CF
When expressed as ₂ -A ³ -Q ² , an electron is attached to the oxygen atom or sulfur atom side Q ¹ ( R ^1- (A ¹ ) _m -Y ¹ ) represented by Z of -Z-CF _2- Place an attractive group on the other side Q ² (R ^2- (A ⁴ ) _n -Y ² )
Is a compound having a structure in which an electron donating group is disposed. The compound used in the present invention has a large dielectric constant as compared to a compound in which Q ¹ is not an electron-withdrawing group or Q ² is not an electron-donating group as shown in JP-A-2-289529. Anisotropy (Δ
ε) can be obtained.

This electron-withdrawing group Q¹-Electron attractionWhen
Is A¹Trans-1,4 in which the remaining hydrogen atoms of are unsubstituted-
ShiClohexylene group or 1,4-HA phenylene group, Y¹
Is a single bond, and R¹Is an electron compared to a hydrogen atom
Means suction.

The electron-withdrawing group Q ¹ -is -OCO-, -CO-
And those having a halogen atom or a cyano group can be used. Specifically, A ¹ and A ^{2 each} have one or more halogen atoms or cyano groups as substituents, Y ¹ is —OCO—, —CO—, or R ¹ is An alkyl group or an alkoxy group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, an acyl group or an alkoxycarbonyl group in which one or more hydrogen atoms may be substituted with a fluorine atom, a halogen atom or A cyano group, part of the carbon-carbon bond of which may be a double bond, or an oxygen atom may be inserted between the carbon-carbon bonds; Sex can be used.

[0014] In the present invention, A ² is one or two or more halogen atoms as substituents, 1,4 has a cyano group - when it is full Eniren group, A ^1, A ² , R ¹ , and Y ¹ may be within the above ranges. Even if Q ¹ − is not an electron-withdrawing group, the same effect as when Q ¹ − is an electron-withdrawing group can be obtained.

This electron donating group Q^Two-Electron donating property ofWhen
Is A^FourTrans-1,4 in which the remaining hydrogen atoms of are unsubstituted-
ShiClohexylene group or 1,4-HA phenylene group, Y^Two
Is a single bond, and R^TwoIs an electron compared to a hydrogen atom
Means donating.

As the electron donating group Q ^2- , those having a nitrogen-containing ring or containing a multiple bond can be used. Specifically, one or more of A ⁴ is present in the group
A group in which the CH group is substituted with a nitrogen atom, or Y ² is -C≡C-,
_{-CH = CH-, -CH 2 CH 2} -, - OCH 2 -, - or CH ₂ is O-, R ² is a double bond or a carbon - which may contain an oxygen atom between carbon bonded carbon An alkyl group or an alkoxy group having a number of 1 to 10, and those having an electron donating property within this range can be used.

The specific structure of the compound of the present invention includes the following compounds as main compounds. Here, Z is an oxygen atom or a sulfur atom as defined above.

A compound having a carbonyl group -CO- on the Q ¹ -side. R ³ -CO-A ² -Z-CF ₂ -Q ² (2) R ³ -CO-A ¹ -A ² -Z-CF ₂ -Q ² (3) R ¹ -A ¹ -CO-A ^2- Z-CF ₂ -Q ² (4) R ¹ -A ¹ -OCO-A ² -Z-CF ₂ -Q ² (5) In addition, R ³ has one or more hydrogen atoms replaced by fluorine atoms. And an alkyl group or an alkoxy group having 1 to 10 carbon atoms. If the electron-withdrawing property is maintained, a double bond or an oxygen atom between carbon-carbon bonds may be contained therein.

More specifically, there are the following compounds. However, in the following, “Ph” has no substituent 1,
Represents a 4-phenylene group, and “Cy” has no substituent;
Shows a cyclohexylene group. R ³ -CO-Ph-Z-CF ₂ -Ph-R ² (2A) R ³ -CO-Ph-Z-CF ₂ -Ph-Ph-R ² (2B) R ³ -CO-Ph-Z-CF ₂ -Ph-C ≡C-Ph-R ² (2C) R ³ -CO-Ph-Z-CF ₂ -Ph-CH = CH-Ph-R ² (2D) R ³ -CO-Ph-Z-CF ₂ -Ph-CH ₂ CH ₂ -R ² (2E) R ³ -CO-Ph-Z-CF ₂ -Ph-OCH ₂ -Ph-R ² (2F) R ³ -CO-Ph-Z-CF _2- Ph-CH ₂ O-Ph-R ² (2G)

R ³ -CO-Ph-Ph-Z-CF ₂ -Ph-R ² (3A) R ³ -CO-Ph-Ph-Z-CF ₂ -Ph-Ph-R ² (3B) R ^3- CO-Ph-Ph-Z-CF ₂ -Ph-CH ₂ CH ₂ -Ph-R ² (3C)

R ¹ -Ph-CO-Ph-Z-CF ₂ -Ph-R ² (4A) R ¹ -Ph-CO-Ph-Z-CF ₂ -Ph-Ph-R ² (4B) R ^1- Ph-CO-Ph-Z-CF ₂ -Ph-CH ₂ CH ₂ -Ph-R ² (4C) R ¹ -Ph-OCO-Ph-Z-CF ₂ -Ph-R ² (5A) R ¹ -Ph -OCO-Ph-Z-CF ₂ -Ph-Ph-R ² (5B)

[0022] In addition, the 1,4 - trans the full Eniren based on
- 1,4 - a compound obtained by replacing the sheet Kurohekishiren group, are as follows. R ³ -CO-Ph-Z-CF ₂ -Cy-R ² (2H) R ³ -CO-Ph-Z-CF ₂ -Ph-Cy-R ² (2I) R ³ -CO-Cy-Ph-Z -CF ₂ -Ph-R ² (3D) R ³ -CO-Ph-Ph-Z-CF ₂ -Ph-Cy-R ² (3E) R ¹ -Cy-CO-Ph-Z-CF ₂ -Ph- R ² (4D) R ¹ -Ph-CO-Ph-Z-CF ₂ -Ph-Cy-R ² (4E) R ¹ -Cy-OCO-Ph-Z-CF ₂ -Ph-R ² (5C) R ¹ -Ph-OCO-Ph-Z-CF ₂ -Cy-R ² (5D)

A compound in which R ¹ on the Q ¹ -side is an alkyl group, alkoxy group, acyl group or alkoxycarbonyl group containing a fluorine atom, or a halogen atom or a cyano group. R ⁴ -A ² -Z-CF ₂ -Q ² (6) R ⁴ -A ¹ -Y ¹ -A ² -Z-CF ₂ -Q ² (7) R ⁴ is one or more hydrogen atoms Is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an acyl group or an alkoxycarbonyl group substituted by a fluorine atom. Also, if the electron-withdrawing nature is maintained, it may contain double bonds therein, a carbon - oxygen atom may be inserted between carbon bond.

More specifically, there are the following compounds. R ⁴ -Ph-Z-CF ₂ -Ph-R ² (6A) R ⁴ -Ph-Z-CF ₂ -Ph-Ph-R ² (6B) R ⁴ -Ph-Z-CF ₂ -Ph-CH ₂ CH ₂ -Ph-R ² (6C) R ⁴ -Ph-Ph-Z-CF ₂ -Ph-R ² (7A) R ⁴ -Ph-Ph-Z-CF ₂ -Ph-Ph-R ² (7B) R ⁴ -Ph-CO-Ph-Z-CF ₂ -Ph-R ² (7C) R ⁴ -Ph-OCO-Ph-Z-CF ₂ -Ph-R ² (7D)

R ⁴ -Ph-Z-CF ₂ -Cy-R ² (6D) R ⁴ -Ph-Z-CF ₂ -Ph-Cy-R ² (6E) R ⁴ -Ph-Z-CF ₂ -Cy -Ph-R ² (6F) R ⁴ -Ph-Z-CF ₂ -Ph-CH ₂ CH ₂ -Cy-R ² (6G) R ⁴ -Cy-Ph-Z-CF ₂ -Ph-R ² (7F ) R ⁴ -Ph-Ph-Z-CF ₂ -Ph-Cy-R ² (7G) R ⁴ -Cy-CO-Ph-Z-CF ₂ -Ph-R ² (7H) R ⁴ -Cy-OCO- Ph-Z-CF ₂ -Ph-R ² (7I)

A compound in which A ² has one or more halogen atoms or cyano groups as a substituent.

[0027]

Embedded image

In the present invention, in addition to the above examples, there are various compounds in which two or more of the above characteristics are combined, and R ^1- (A ¹ ) _m -Y ^1-
Is an electron-withdrawing group, or A ² has one or more halogen atoms or cyano groups as substituents, and R ^2- (A ⁴ ) _n -Y ² -has an electron donating property. Any group can be used.

The compound of the formula (1) of the present invention is used as a liquid crystal composition by mixing at least one compound with other liquid crystals and non-liquid crystals. Examples of the substance which is mixed with the compound of the present invention to form a liquid crystal composition include the following. 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.

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

[0032]

Embedded image

It should be noted that these compounds merely exemplification
Ri, halogen atom of the hydrogen atoms of the ring structure or terminal groups,
Substitution to cyano group, methyl group, etc., substitution of cyclohexane ring, benzene ring to other six-membered ring, five-membered ring, etc., change of bonding group between rings, etc. are possible, according to desired performance Various materials may be selectively used.

The liquid crystal composition of the present invention is disposed between substrates having electrodes, and is provided with a twisted nematic system, a guest-host system,
Dynamic scattering method, phase change mode, DAP mode, cut with a <br/> used in dual frequency mode, a ferroelectric liquid crystal display system such as a variety of modes. In particular, when used in a liquid crystal display device driven in a time-division manner, the advantage is great.

Specifically, the following are typical. On a substrate such as plastic or glass as required
After forming an undercoat layer such as SiO ₂ and Al ₂ O ₃ and a color filter layer, providing electrodes such as In ₂ O ₃ -SnO ₂ (ITO) and SnO ₂ and patterning, if necessary, polyimide and polyamide , SiO _2, Al ₂ O ₃ or the like overcoat layer formation, alignment treatment, which sealing material is printed on, to seal the peripheral electrode surface is disposed so as to face each other, and curing the sealing material To form empty cells.

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

[0037] Incidentally, the above description should not only showing a basic configuration and manufacturing method of the liquid crystal display device, for example a substrate using a two-layer electrode, two-layer liquid crystal cell forming the liquid crystal layer of the two layers , An active matrix element using an active matrix substrate on which active elements such as TFTs and MIMs are formed,
Various configurations can be used.

Since the liquid crystal composition of the present invention improves the time-division characteristics, it is suitable for a liquid-crystal display device driven in a time-division manner.
In particular, the effect is great when driving at a high duty ratio. Therefore, the present invention is also suitable for a super twist (STN) type liquid crystal display device having a high twist angle, which has attracted attention in recent years.

The compound of the general formula (1) used in the present invention is produced, for example, according to the following method. At this time, a part of the compound represented by the general formula (1) will be described as Q ³ -Z-CF ₂ -Q ⁴ . Q ³
Is Q ¹ -A ² described above, that is, R ^1- (A ¹ ) _n -Y ¹ -A ² . Q ⁴ is Q ²
-A ³ , that is, R ^2- (A ⁴ ) _n -Y ² -A ³ .

When Z is an oxygen atom, it is produced according to the following method. Q ³ -OH (8) ↓ Q ⁴ -CH ₂ X (9) Q ³ -O-CH ₂ -Q ⁴ (10) ↓ Cl ₂ (11) Q ³ -O-CCl ₂ -Q ⁴ (12) ↓ KF (13) Q ³ -O-CF ₂ -Q ⁴ (14)

The compound (8) represented by Q ³ -OH and the halogen compound (9) are reacted under a basic condition such as an alkali metal hydroxide to obtain a compound (10). This compound (10) is reacted with chlorine gas (11) to give a dichloromethylene group-containing compound.
(12), which can be reacted with potassium fluoride (13) without isolation and purification to obtain the desired compound (14).

There is also the following manufacturing method. Q ³ -O-CO-Q ⁴ (15) ↓ P ₂ S ₅ (16) Q ³ -O-CS-Q ⁴ (17) ↓ DAST (18) Q ³ -O-CF ₂ -Q ⁴ (14)

That is, the ester compound (15) is reacted with phosphorus pentasulfide (16) as a thiocarbonylating agent to obtain a thioester compound (17). Which is reacted with diethylaminosulfur triflate Ruori de a fluorinating agent (DAST) (18), can be obtained difluoro ether compound (14).

When Z is an oxygen atom or a sulfur atom, A. Haas et al., Chemical Berichte Vol.
The following reaction route described in pp. 1329 (1988) is also possible. Q ⁴ -CHO (19) ↓ DAST (20) Q ⁴ -CF ₂ H (21) ↓ Br ₂ (22) Q ⁴ -CF ₂ Br (23) ↓ Q ³ -ZH (24) Q ³ -Z-CF ₂ -Q ⁴ (25)

That is, the aldehyde compound (19) is fluorinated with DAST (20) to give a difluoromethyl group-containing compound (21), and then the bromine (22) is substituted by photobromination to give the bromodifluoro compound (23). The resulting compound (24) is reacted with compound (24) in the presence of a base to give desired compound (25).

Further, it can be produced as follows using a compound having a trichloromethyl group as a starting material. Q ⁴ -CCl ₃ (26) ↓ HF (27) Q ⁴ -CF ₂ Cl (28) ↓ Q ³ -ZH (29) Q ³ -Z-CF ₂ -Q ⁴ (30)

That is, the trichloromethyl compound (26) is reacted with hydrofluoric acid (27) and pyridine to obtain a chlorodifluoromethyl compound (28), which is reacted with the compound (29) in the presence of a base to give the desired compound. (30) can be obtained.

Further, using the above basic reaction,
Q^3A-Z-CF_Two-Q^4A Basic skeleton (however, Q^3A , Q^4A Is
Q each^Three, Q^FourMay be the same asatom, Hydroxyl
Analogous compounds having groups, halogen atoms, etc.
is there. ) Can be synthesized and then converted to a functional group.Can
You. Changes during the above basic reaction among the compounds used in the present invention
If it contains functional groups that cause
Then, a desired functional group is introduced. Specifically,
When the chlorination reaction is performed as in the first example,
When it contains an organic group that can react with^3A-
Z-CF_Two-Q^4A Compound of the formula
Should be introduced.

When the terminal R ¹ is a fluorine atom, for example, the following method may be used. Cl-Ph-O-CF ₂ -Ph-R ² (31) ↓ KF (32) F-Ph-O-CF ₂ -Ph-R ² (33)

A compound (31) in which R ^{1 at} the terminal of Q ³ is chlorine is synthesized by the basic reaction as described above, and
With 2-20 times the potassium fluoride (32), R ¹ of interest to fluorination to give a compound of fluorine atoms (33). The fluorination reaction, as a solvent, sul ho runs relatively well dissolved potassium fluoride, it is preferable to use aprotic polar solvents such as Jimechirusuru ho alkoxy <br/> de, phosphorus or nitrogen atom as a reaction catalyst It is preferable to use a phase transfer catalyst containing

When the terminal R ² is substituted with an alkyl group or an alkenyl group, for example, the following may be performed. R ¹ -Ph-O-CF ₂ -Ph-Cl (34) ↓ R ² MgBr (35) R ¹ -Ph-O-CF ₂ -Ph-R ² (36)

[0052] R ² is a compound of chlorine at the end of Q ⁴ (34) to leave synthesized in basic reaction as described above, which in ether, the ether solvent in the alkyl Gurini catcher <br/> Lumpur tetrahydrofuran is reacted with reagent (35), it is possible to obtain the desired compound (36) (e.g., Bulletin of the Chemical S
society of Japan, vol. 49, 1958-1969, 1967). In this case, a bivalent catalyst having a phosphine as a ligand is preferably used as the nickel catalyst.

The introduction of an oxycarbonyl group on the benzene ring, that is, the introduction of —OCO— into Y ¹ can be performed, for example, by oxidizing the alkyl group using a compound having an alkyl group at the terminal as a starting material. A compound having a phenolic hydroxyl group at a terminal is produced. This compound is converted to R ² -Ph-CF ₂ -O-
It can be synthesized by reacting with an acid chloride represented by Ph-COCl 2 in the presence of a base.

The reaction for introducing an acyl group onto a benzene ring is performed, for example, by adding a compound in which R ² is a hydrogen atom to R ² —COCl or R ²
It can be obtained by Friedel-Crafts reaction with an acid chloride represented by -Ph-COCl.

[0055] The reaction for introducing a cyano group on the benzene ring, for example, to synthesize a compound having a halogen atom on the benzene ring, it is possible to obtain by reacting with copper cyanide halogen atom (e.g. MSNewman, Organic
Synthesis vol.3, pp.631). Alternatively, a compound having a cyano group can be synthesized by synthesizing a compound having an amide group and dehydrating the amide group with a dehydrating agent such as phosphorus pentachloride.

[0056] The above production method is merely exemplary,
Various production methods can be used depending on the reaction order, combination, and the like. Hereinafter, a method for producing the compound of the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0057]

Example 1 In a 500 ml glass three-necked flask equipped with a reflux tube, 25.0 g (0.12 mol) of p-chlorobenzyl bromide and 12.2 g of phenol were added.
(0.13 mol), potassium carbonate 18.5 g (0.13 mol), acetone 100
ml was charged and refluxed for 4 hours. After cooling, the inorganic salts were filtered off and the filtrate was poured into 500 ml of water. Separate the organic layer,
After washing it with 5% NaHCO ₃ aqueous solution and then with water,
Dried over MgSO ₄ . After filtration, the solvent was distilled off, the resulting solid was recrystallized from methyl alcohol, 4-chlorobenzyl ether _{(H- Ph-O-CH 2} -Ph-Cl) and 23.1 g (yield
88%).

Next, a reflux condenser and gas blow with a tube 100ml
Of glass three-neck flask 4 Kurorobenji Ruch phenyl ether 21.9 g (0.1 mol) and was charged with phosphorus pentachloride 3.51 g,
Heated to 100 ° C. Here, 40g of chlorine gas and reaction temperature
Blowing was performed over 2 hours while maintaining the temperature at 100 to 150 ° C. After cooling, nitrogen gas was blown in for 30 minutes, and then 16 g of spray-dried potassium fluoride which had been dried in vacuo in advance was added.
The reaction was carried out at 180 ° C. for 5 hours with vigorous stirring. After cooling, methylene chloride was added, the inorganic salts were filtered off, the filtrate was washed with water, the solvent was distilled off, and the solid obtained was recrystallized from methyl alcohol to give 4-chloro-α, α-difluorobenzyl. 12.9 g of phenyl ether (0.051 mol, 51% yield,
45%). H-Ph-O-CF ₂ -Ph-Cl

The analysis results of this compound are shown below. ¹⁹ F NMR (CDCl ₃ ) -65.9 ppm (-CF ₂ -O-, S) MS m / e 254 (M ⁺ ) IR 1205 cm ^-1 (CF)

Under an argon atmosphere, 2.02 g (0.083 mol) of Mg and 10 ml of dry tetrahydrofuran (THF) were placed in a 100 ml three-necked flask equipped with a reflux tube, and several drops of 1-bromopropane were added thereto. Then, 9.36 g (0.076 mol) of 1-bromopropane
Was added dropwise at a rate that maintained the exotherm. After the completion of the dropwise addition, the mixture was further refluxed for 1 hour and then allowed to cool to room temperature. This solution was separately placed in a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere, and 10 g (0.039 mol) of 4-chloro-α, α-difluorobenzylphenyl ether synthesized as described above was added. 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl ₂ (dppp)] 1.0g dry THF solution 20ml
Was added dropwise using a dropping funnel.

[0061] After refluxing dropwise After a further 24 hours, cooled to room temperature, water was added 20 ml. The organic layer was separated further by adding 20% hydrochloric acid 20 ml, washed with water, dried and evaporated. The obtained crude product was purified by silica gel column chromatography to obtain 8.07 g (79% yield) of 4-n-propyl-α, α-difluorobenzylphenyl ether. H-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

The analysis results of this compound are shown below. ¹⁹ F NMR (CDCl ₃ ) -67.0 ppm (-CF ₂ -O-, S) MS m / e 262 (M ⁺ ) IR 1205 cm ^-1 (CF)

Under an argon atmosphere, 50 ml of methylene chloride and 4.75 ml of aluminum chloride were placed in a 300 ml three-necked flask equipped with a reflux tube.
5 g (0.035 mol), 4-n-propyl-α, α- synthesized above
6.6 g (0.025 mol) of difluorobenzyl phenyl ether
Input is cooled to 0 ° C.. 3.7 g (0.035 mol) of butyric acid chloride diluted with 25 ml of methylene chloride was added dropwise thereto. After further reacting at 15 ° C. for 2 hours, the reaction was stopped by adding water.

After separating the organic layer, the aqueous layer was extracted with methylene chloride and added to the organic layer. The organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate.
After concentrating the organic layer, it is purified by silica gel column chromatography using hexane as a mobile phase, and 4-n-propyl-α, α
-Difluorobenzyl-4'-butyrylphenyl ether 6.
1 g (0.0183 mol, 73% yield) was obtained. nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0065]

Embedded image

The analysis results of this compound are shown below. ¹⁹ F NMR (CDCl ₃ ) -67.2 ppm (-CF ₂ -O-, S) MS m / e 332 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 1. CH ₃ -CO-Ph-O-CF ₂ -Ph-CH ₃ nC ₅ H ₁₁ -CO-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) nC ₈ H ₁₇ -CO-Ph-O- CF ₂ -Ph-C ₈ H ₁₇ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Cy -C ₃ H ₇ (n)

Example 2 In place of 1-bromopropane used for 4-chloro-α, α-difluorobenzylphenyl ether of Example 1,
Using bromo-trans-4-n-propylcyclohexane, α, α-difluoro-4- (4′-n-propylcyclohexyl) benzylphenyl ether was obtained. (54% yield)

This was reacted with butyric acid chloride in the same manner as in Example 1 to obtain α, α-difluoro-4- (4′-n-propylcyclohexyl) benzyl-4-n-butyrylphenyl ether. (Yield 64%) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ (n)

[0070]

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The analysis results of this compound are shown below. MS m / e 414 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 2. CH ₃ -CO-Ph-O-CF ₂ -Ph-Cy-CH ₃ nC ₅ H ₁₁ -CO-Ph-O-CF ₂ -Ph-Cy-C ₅ H ₁₁ (n) nC ₈ H ₁₇ -CO- Ph-O-CF ₂ -Ph-Cy-C ₈ H ₁₇ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-Cy-C ₅ H ₁₁ (n)

Example 3 In place of 1-bromopropane used for 4-chloro-α, α-difluorobenzylphenyl ether of Example 1, p-
Using bromotoluene, α, α-difluoro-4- (4′-
Methylphenyl) benzylphenyl ether was obtained.
This was reacted with butyric acid chloride in the same manner as in Example 1 to obtain α, α-difluoro-4- (4′-methylphenyl) benzyl-4-n-butyrylphenyl ether. . (57% yield) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-Ph-CH ₃

[0074]

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The analysis results of this compound are shown below. MS m / e 380 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 3. CH ₃ -CO-Ph-O-CF ₂ -Ph-Ph-CH ₃ nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -CO- Ph-O-CF ₂ -Ph-Ph-C ₅ H ₁₁ (n) nC ₈ H ₁₇ -CO-Ph-O-CF ₂ -Ph-Ph-C ₈ H ₁₇ (n) nC ₃ H ₇ -CO- Ph-O-CF ₂ -Ph-Ph-C ₅ H ₁₁ (n)

Example 4 Instead of 1-bromopropane used in Example 1 for 4-chloro-α, α-difluorobenzylphenyl ether,
Using bromo-1-propene, α, α-difluoro-4-
(2′-Propenyl) benzyl phenyl ether was obtained.
This was reacted with butyric acid chloride in the same manner as in Example 1 to give 4- (2 ″ -n-propenyl) -α, α-difluorobenzyl-4′-n-butyrylphenyl ether. I got
(Yield 60%) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-CH ₂ CH = CH ₂

[0078]

Embedded image

The analysis results of this compound are shown below. MS m / e 330 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 4. CH ₃ -CO-Ph-O-CF ₂ -Ph-CH ₂ CH = CH ₂ nC ₅ H ₁₁ -CO-Ph-O-CF ₂ -Ph-CH ₂ CH = CH ₂ nC ₈ H ₁₇ -CO-Ph -O-CF ₂ -Ph-CH ₂ CH = CH ₂ nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-CH ₂ CH ₂ CH ₂ CH = CH ₂

Example 5 The reaction of 4-n-propyl-α, α-difluorobenzylphenyl ether of Example 1 with trans-2-butenoic acid chloride gave α, α-difluoro-4-n-propylbenzyl. -4 '- (2-butene Neu) phenyl ether. This compound had a double bond in R ¹ , but R ¹ was an electron-withdrawing group as a whole. (E) -CH ₃ CH = CH-CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0082]

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The analysis results of this compound are shown below. MS m / e 330 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 5. (E) -CH ₃ CH = CH-CO-Ph-O-CF ₂ -Ph-CH ₃ (E) -CH ₃ CH = CH-CO-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n ) (E) -CH ₃ CH = CH-CO-Ph-O-CF ₂ -Ph-C ₈ H ₁₇ (n)

Example 6 In the same manner as in Example 1 except that pn-propylbenzoic acid chloride was used instead of butyric acid chloride, α, α-difluoro
-4-n-Propylbenzyl-4 '-(4 "-n - propylbenzoyl) phenyl ether was obtained. (Yield 65%) nC ₃ H ₇ -Ph-CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0086]

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The analysis results of this compound are shown below. MS m / e 408 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 6. CH ₃ -Ph-CO-Ph-O-CF ₂ -Ph-CH ₃ nC ₅ H ₁₁ -Ph-CO-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) nC ₃ H ₇ -O- Ph-CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n) CH ₃ -OC ₂ H ₅ -Ph-CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n) nC ₃ H ₇ -Ph-CO-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) nC ₃ H ₇ -Ph-CO-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ ( n)

Example 7 In the same manner as in Example 1, except that trans-4-n-propylcyclohexanecarboxylic acid chloride was used instead of butyric acid chloride, α, α-difluoro-4-n-propylbenzyl-
4 to obtain a '- - (trans -4' 'n-propyl-cyclohex-Cyr-carbonitrile <br/>) phenyl ether. (Yield 38%) nC ₃ H ₇ -Cy-CO-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0090]

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The analysis results of this compound are shown below. MS m / e 414 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

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

Example 8 4-n-propylphenylacetylene in diethyl ether
It was reacted with equimolar butyllithium at 0 ° C. to form a lithium salt. This was reacted with 4-chloro-α, α-difluorobenzylphenyl ether of Example 1 to obtain α, α-difluoro-4- [2- (4′-n-propylphenyl) ethynyl] benzylphenyl ether. Was. (35% yield)

Then, butyric acid chloride was reacted in the same manner as in Example 1 to obtain α, α-difluoro-4- [2- (4′-n-propylphenyl) ethynyl] benzyl-4 ″ -n-butyl. Ryl phenyl ether was obtained. (Yield 43%) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-C ≡C-Ph-C ₃ H ₇ (n)

[0095]

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The analysis results of this compound are shown below. MS m / e 432 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O), 2120 cm ^-1 (C≡C)

The following compounds can be synthesized in the same manner as in Example 8. CH ₃ -CO-Ph-O-CF ₂ -Ph-C≡C-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -CO-Ph-O-CF ₂ -Ph-C≡C-Ph-C ₃ H ₇ (n) nC ₈ H ₁₇ -CO-Ph-O-CF ₂ -Ph-C≡C-Ph-C ₃ H ₇ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph -C ≡C-Ph-C ₅ H ₁₁ (n)

Example 9 Trans-2- (4-n-propylphenyl) -1-bromoethene was reacted with an equimolar amount of butyllithium in dry THF at -78 ° C to give a lithium salt. This was reacted at -50 ° C with the 4-chloro-α, α-difluorobenzylphenyl ether of Example 1 to give α, α-difluoro-4- [trans-2- (4′-n-
Propylphenyl) ethenyl] benzylphenyl ether was obtained. (Yield 32%)

Then, butyric acid chloride was reacted in the same manner as in Example 1 to obtain α, α-difluoro-4- [2- (4′-n-propylphenyl) ethenyl] benzyl-4 ″ -n-butyl. Ryl phenyl ether was obtained. (Yield 66%) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph-CH = CH-Ph-C ₃ H ₇ (n)

[0100]

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The analysis results of this compound are shown below. MS m / e 434 (M ⁺ ) IR 1200 cm ^-1 (CF), 1680 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 9. CH ₃ -CO-Ph-O-CF ₂ -Ph-CH = CH-Ph-C ₃ H ₇ (n) nC ₅ H ₁₁ -CO-Ph-O-CF ₂ -Ph-CH = CH-Ph-C ₃ H ₇ (n) nC ₈ H ₁₇ -CO-Ph-O-CF ₂ -Ph-CH = CH-Ph-C ₃ H ₇ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Ph -CH = CH-Ph-C ₅ H ₁₁ (n)

In the same manner as in Examples 1 to 9, the following compounds can be synthesized. nC ₃ H ₇ -CO-Ph-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n) nC ₃ H ₇ -CO-Ph-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ ( n) nC ₃ H ₇ -CO-Ph-Cy-O-CF ₂ -Ph-C ₃ H ₇ (n) nC ₃ H ₇ -CO-Ph-O-CF ₂ -Cy-CH = CH-Ph-C ₃ H ₇ (n)

Example 10 Using p-fluorophenol in place of phenol of Example 1, α, α-difluoro-4-chlorobenzyl-4′-
Fluorophenyl ether was obtained. (Yield 55%)
Reacting 1-bromopropane to form α, α-difluoro-4
-n-Propylbenzyl-4'-fluorophenyl ether was obtained. (61% yield) F-Ph-O-CF 2 -Ph-C 3 H 7 (n)

[0105]

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The analysis results of this compound are shown below. MS m / e 280 (M ⁺ ) IR 1200 cm- ¹ (CF)

In the same manner as in Example 10, the following compounds can be synthesized. F-Ph-O-CF ₂ -Ph-CH ₃ F-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) F-Ph-O-CF ₂ -Ph-C ₈ H ₁₇ (n)

Instead of 1-bromopropane, 1-bromo-4
The following compounds can also be synthesized using -n-propylbenzene, trans-1-bromo-4-n-propylcyclohexane, and the like. F-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) F-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ (n) F-Ph-O-CF ₂ -Ph -CH ₂ CH ₂ -C ₃ H ₇ (n)

Example 11 Using 4- (4′-fluorophenyl) phenol instead of phenol of Example 1, α, α-difluoro-4-chlorobenzyl-4 ′-(4 ″ -fluorophenyl) Phenyl ether was obtained. This was reacted with 1-bromopropane to give α, α-difluoro-4-n-propylbenzyl.
-4 ′-(4 ″ -fluorophenyl) phenyl ether was obtained. (63% yield) F-Ph-Ph-O -CF 2 -Ph-C 3 H 7 (n)

[0110]

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The analysis results of this compound are shown below. MS m / e 356 (M ⁺ ) IR 1200 cm- ¹ (CF)

The following compounds can be synthesized in the same manner as in Example 10. F-Ph-Ph-O-CF ₂ -Ph-CH ₃ F-Ph-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) F-Ph-Ph-O-CF ₂ -Ph-C ₈ H ₁₇ (n)

Instead of 1-bromopropane, 1-bromo-4
The following compounds can also be synthesized using -n-propylbenzene, trans-1-bromo-4-n-propylcyclohexane, and the like. F-Ph-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) F-Ph-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ (n) F-Ph-Ph- O-CF ₂ -Ph-CH ₂ CH ₂ -C ₃ H ₇ (n)

Example 12 Using p-trifluoromethylphenol instead of phenol of Example 1, α, α-difluoro-4-chlorobenzyl-4 ′-(4 ″ -trifluoromethylphenyl) phenyl ether I got This was reacted with 1-bromopropane to obtain α, α-difluoro-4-n-propylbenzyl-4 ′-(4 ″ -trifluoromethylphenyl) phenyl ether. (Yield 57%) CF ₃ -Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0115]

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The analysis results of this compound are shown below. MS m / e 330 (M ⁺ ) IR 1200 cm- ¹ (CF)

Example 13 α, α-Difluoro-4-chlorobenzyl-4 ′-(4 ″ -trifluoromethoxyphenyl) phenyl ether was obtained by substituting p-trifluoromethoxyphenol for phenol in Example 1. I got This was reacted with 1-bromopropane to give α, α-difluoro-4-n-propylbenzyl-4 ′-(4 ″ -trifluoromethoxyphenyl).
Phenyl ether was obtained. (51% yield). CF ₃ O-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0118]

Embedded image

The analysis results of this compound are shown below. MS m / e 346 (M ⁺ ) IR 1200 cm- ¹ (CF)

The following compounds can be synthesized in the same manner as in Example 12 or 13. CF ₃ -Ph-Ph-O-CF ₂ -Ph-CH ₃ CF ₃ O-Ph-Ph-O-CF ₂ -Ph-CH ₃ CF ₃ -Ph-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) CF ₃ O-Ph-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) CF ₃ -CH ₂ -Ph-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n) CF ₃ -CH ₂ -O-Ph-Ph-O-CF ₂ -Ph-C ₅ H ₁₁ (n)

Instead of 1-bromopropane, 1-bromo-4
The following compounds can also be synthesized using -n-propylbenzene, trans-1-bromo-4-n-propylcyclohexane, and the like. CF ₃ -Ph-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) CF ₃ -Ph-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ (n) CF ₃ -Ph -Ph-O-CF ₂ -Ph-CH ₂ CH ₂ -C ₃ H ₇ (n) CF ₃ O-Ph-Ph-O-CF ₂ -Ph-Ph-C ₃ H ₇ (n) CF ₃ O- Ph-Ph-O-CF ₂ -Ph-Cy-C ₃ H ₇ (n) CF ₃ O-Ph-Ph-O-CF ₂ -Ph-CH ₂ CH ₂ -C ₃ H ₇ (n)

Example 14 Compound 4-n-propyl-α, α-difluorobenzyl-4′-butyrylphenyl ether synthesized in Example 1 4 g (0.01 g)
2 mol) and 20 ml of benzene were placed in a 200 ml three-necked flask equipped with a reflux tube, and 3 ml of concentrated sulfuric acid was added thereto. Azide here
While slowly adding 22.5 ml of a benzene solution of 0.9 g of hydrogen, 40
The reaction was performed at a temperature of 1 hour.

After cooling, the mixture was slowly poured into water and extracted with ether. After the ether layer was neutralized, the solid obtained after drying and distilling off the solvent was transferred again to a 100 ml flask equipped with a reflux tube, and 20 ml of concentrated hydrochloric acid was added thereto, followed by refluxing for 2 hours. Pour the contents into water and extract with ether.
Washed with 10% aqueous sodium hydroxide. After drying, the solvent was distilled off to obtain a crude product. Recrystallization from hexane gave 1.0 g (0.0036 mol) of 4-n-propyl-α, α-difluorobenzyl-4′-aminophenyl ether. (Yield 30%) H ₂ N-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

The whole amount of the obtained compound was transferred to a 100 ml reactor, 5 ml of concentrated hydrochloric acid and 10 ml of water were added, and the mixture was stirred at 40 ° C. for 15 minutes and then cooled to 0 ° C. Was slowly added dropwise here an aqueous solution 5g of sodium nitrite 0.34g as the temperature in the system not be exceeded 4 ° C.. After the addition was completed, the solution was stored at 0 ° C. Another 200ml
1.4 g of potassium cyanide, 0.3 g of sodium hydroxide, 20 ml of water and 10 ml of benzene were placed in a three-necked flask, and 10 ml of an aqueous solution of 1.6 g of nickel nitrite was added dropwise thereto. The previously prepared diazonium solution was added dropwise to the reaction solution at 5 ° C or lower. After the dropwise addition, the mixture was stirred at this temperature for 30 minutes, and then reacted at room temperature for 2 hours.

The benzene layer was separated, and the aqueous layer was extracted with ether. The combined organic layers were washed with water, dried and the solvent was distilled off. The crude product was purified by silica gel column chromatography (mobile phase: hexane / dichloromethane 5/1 by volume) to give the desired compound 4-n-propyl-α. There was obtained 0.4 g (0.0014 mol) of α, difluorobenzyl-4′-cyanophenyl ether. (Yield 38%) NC-Ph-O-CF ₂ -Ph-C ₃ H ₇ (n)

[0126]

Embedded image

The analysis results of this compound are shown below. MS m / e 287 (M ⁺ ) IR 1205 cm ^-1 (CF), 2210 cm ^-1 (C≡N)

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

Example 15 In a 200 ml Hastelloy autoclave, 100 g (0.434 mol) of 4-chlorobenzotrichloride, hydrofluoric acid (70 wt%) / pyridine
(30 wt%) 49.6 g of the complex was added and reacted at 80 ° C. for 5 hours. The reaction was cooled to room temperature, transferred to a separatory funnel and the lower layer was collected. Lower further washed with 5% aqueous sodium hydrogen carbonate solution, distilled under reduced pressure, 4-chloro - give the chloro difluoro-methylol behenate <br/> benzene 47.4g (0.241mol). CClF ₂ -Ph-Cl

In a 1000 ml four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, sodium hydride (60 mL) was added.
%) And 100 ml of N, N-dimethylformamide (DMF) were added, and the mixture was cooled to 5 ° C. in an ice bath under a nitrogen stream. Leakage dropping to there
A solution of 25.0 g (0.14 mol) of p- (α, α, α-trifluorotoluene) thiol in 250 ml of DMF was added dropwise from the funnel. After completion of the dropwise addition, the mixture is further stirred at room temperature for 1 hour , and p- (α, α, α-
(Trifluorotoluene) Thiol sodium salt DFM solution
Was prepared .

A separately prepared stirrer, cooling tube, dropping funnel ,
In a 1000 ml four-necked flask equipped with a thermometer, 19.5 g of the above synthesized 4-chloro-chlorodifluoromethylbenzene (0.
(1 mol) dissolved in 75 ml of DMF was added and heated to 80 ° C. P- prepared here above (alpha, alpha, alpha-trifluorotoluene) thiol Luna the total amount of DMF solution of thorium salt was added and reacted for 3 hours. After adding water to stop the reaction, the organic layer was separated. The aqueous layer was extracted with methylene chloride, and dried with anhydrous magnesium sulfate together with the organic layer.

After filtration, the solvent was distilled off, and the crude product was purified by silica gel column chromatography using hexane as a mobile phase to give α, α-difluoro-4-chlorobenzyl-4′-.
12.6 g of trifluoromethylphenylthioether (0.0372
mol). (Yield 37%) CF ₃ -Ph-S-CF ₂ -Ph-Cl

The analysis results of this compound are shown below. ¹⁹ F NMR δppm from CFCl ₃ -71.9 ppm ( -S-CF _2- , S),-65.0 ppm (CF ₃ , S) ¹ H NMR (CDCl ₃ ) δppm from TMS 7.18 ppm ~ 7.53 ppm (Ph, 8H, m) MS m / e 338 (M ⁺ ) IR 1205 cm- ¹ (CF)

In an argon atmosphere, 0.3 g (0.012 mol) of Mg and 10 ml of dry THF were placed in a 100 ml three-necked flask equipped with a reflux tube. Then, 1.2 g (10 mol) of 1-bromopropane was added dropwise at such a rate that the heat generation continued. After the completion of the dropwise addition, the mixture was further refluxed for 1 hour, and then allowed to cool to room temperature. This solution was separately placed in a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere, and the α, α-difluoro-4-chlorobenzyl
2.4 g of -4'-trifluoromethylphenylthioether (0.0
07Mol) and 1,3-bis (diphenylphosphino) propane dichloronickel [NiCl ₂ (dppp)] Drying TH containing 0.15g
The F solution 20 ml, was added dropwise using a dropping funnel.

[0135] After refluxing dropwise After a further 24 hours, cooled to room temperature, water was added 20 ml. The organic layer was separated further by adding 20% hydrochloric acid 20 ml, washed with water, dried and evaporated. The obtained crude product was purified by silica gel column chromatography to obtain α, α-difluoro-4-n-propylbenzyl.
0.99 g of -4'-trifluoromethylphenylthioether was obtained. (Yield 41%) CF ₃ -Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

[0136]

Embedded image

The analysis results of this compound are shown below. ¹⁹ F NMR -72.0 ppm (-S-CF _2- , S) -65.0 ppm (CF ₃ , S) MS m / e 346 (M ⁺ ) IR 1205 cm ^-1 (CF)

In the same manner as in Example 15, the following compounds can be synthesized. C ₂ F ₅ -Ph-S-CF ₂ -Ph-C ₃ H ₇ (n) CF ₃ -Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) CF ₃ -Ph-S-CF _2- Ph-Ph-C ₃ H ₇ (n)

Example 16 p- (α, α, α-trifluorotoluene) of Example 15
Instead of thiol, use p-fluorobenzenethiol and use 4- n- propyl-chlorodifluoromethylbenzene instead of 4 - chloro-chlorodifluoromethylbenzene to obtain α, α-difluoro-4-n-propyl Benzyl-
4-Fluorophenylthioether was obtained. (Yield 55
%) F-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

[0140]

Embedded image

The analysis results of this compound are shown below. MS m / e 296 (M ⁺ ) IR 1205 cm- ¹ (CF)

Example 17 p- (α, α, α-trifluorotoluene) of Example 15
Instead of thiol, use p-fluorophenylbenzenethiol, use 4- n- propyl-chlorodifluoromethylbenzene instead of 4 - chloro-chlorodifluoromethylbenzene, and use α, α-difluoro-4-n- Propylbenzyl-4- (4'-fluorophenyl) phenylthioether was obtained. (60% yield) F-Ph-Ph-S -CF 2 -Ph-C 3 H 7 (n)

[0143]

Embedded image

The analysis results of this compound are shown below. MS m / e 372 (M ⁺ ) IR 1205 cm- ¹ (CF)

In the same manner as in Example 16 or 17, the following compounds can be synthesized. F-Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) F-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n) F-Ph-Ph-S-CF ₂ -Ph -C ₅ H ₁₁ (n) F-Ph-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n)

Example 18 p- (α, α, α-trifluorotoluene) of Example 15
Instead of thiol, p-trifluoromethoxybenzenethiol is used, and instead of 4 - chloro-chlorodifluoromethylbenzene, 4 -n- propyl-chlorodifluoromethylbenzene is used, α, α-difluoro-4-n -Propylbenzyl-4-trifluoromethoxyphenylthioether was obtained. (Yield 63%) CF ₃ O-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

[0147]

Embedded image

The analysis results of this compound are shown below. MS m / e 362 (M ⁺ ) IR 1205 cm- ¹ (CF)

In the same manner as in Example 18, the following compound can be synthesized. C ₂ F ₅ O-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n) C ₃ F ₇ O-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

Example 19 p- ( α, α, α-trifluorotoluene ) of Example 15
The reaction was conducted under the same reaction conditions except that benzenethiol was used instead of thiol, and the compound α, α-difluoro
-4-Chlorobenzyl-phenylthioether was synthesized. (Yield 45%) Ph-S-CF ₂ -Ph-Cl

Further, the same compound as in Example 15 was obtained from this compound.
α, α-Difluoro-4-n-propylbenzyl-phenylthioether was obtained by coupling reaction of n -propylmagnesium bromide. (Yield 61%) Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

In an argon atmosphere, 20 ml of methylene chloride, aluminum chloride,
Α, α-difluoro-4-n-
Propylbenzyl-phenylthioether 2.8g (0.01mo
l) and cooled to 0 ° C. 1.6 g (0.015 mol) of butyric acid chloride diluted with methylene chloride was added dropwise thereto. After further reacting at 15 ° C. for 2 hours, the reaction was stopped by adding water.

After separating the organic layer, the aqueous layer was extracted with methylene chloride and added to the organic layer. The organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate.
After concentrating the organic layer, the mixture is purified by silica gel column chromatography using hexane as a mobile phase, and α, α-difluoro-4
2.1 g of -n-propylbenzyl-4'-butyrylphenylthioether was obtained. (Yield 60%) nC ₃ H ₇ -CO-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

[0154]

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The analysis results of this compound are shown below. ¹⁹ F NMR (CDCl ₃ ) δ ppm from CFCl ₃ -71.7 ppm (-SC F _2- , S) MS m / e 348 (M ⁺ ) IR 1205 cm ^-1 (CF), 1685 cm ^-1 (C = O)

The following compounds can be synthesized in the same manner as in Example 19. CH ₃ -CO-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n) nC ₃ H ₇ -CO-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n) nC ₃ H ₇ -Ph-CO-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

Example 20 p- (α, α, α-trifluorotoluene) of Example 15
Use p-bromobenzenethiol instead of thiol and α, α-difluoro-4-n-propyl using 4-n-propyl-chlorodifluoromethylbenzene instead of 4 - chloro-chlorodifluoromethylbenzene Benzyl
-4'-Bromophenylthioether was obtained. (69% yield) Br-Ph-S-CF 2 -Ph-C 3 H 7 (n)

[0158]

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The analysis results of this compound are shown below. MS m / e 356 (M ⁺ ), 358 (M ⁺ ) IR 1205 cm- ¹ (CF)

Subsequently, the liquid crystal compound precursor (α, α-difluoro-4-n-propyl) prepared above was placed in a 100 ml four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer.
Benzyl-4'-bromophenylthioether) 3.6 g (0.0
1 mol), 1.8 g (0.02 mol) of finely ground copper cyanide and 10 ml of pyridine were added in this order. The mixture was stirred at 150 ° C. for 10 hours, cooled to 80 ° C., and 8 ml of 14% aqueous ammonia was added.
Toluene (10 ml) was added, and the mixture was stirred at room temperature for 30 minutes. 15 ml of ether were added and the reaction mixture was filtered through a glass filter.

The filtrate was separated, the aqueous layer was extracted twice with ether, and the combined organic layers were washed with 5% aqueous ammonia and water. The organic layer was dried over magnesium sulfate, concentrated,
Silica gel column chromatography (mobile phase hexane /
Purification by dichloromethane 10/2 volume ratio), a desired compound having a cyano group alpha, give the α- difluoro -4-n-propyl-benzyl-4'-cyanophenyl thioether 1.0 g. (33% yield) NC-Ph-S-CF 2 -Ph-C 3 H 7 (n)

[0162]

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The analysis results of this compound are shown below. MS m / e 303 (M ⁺ ) IR 1205 cm ^-1 (CF), 2210 cm ^-1 (C≡N)

The following compounds can be synthesized in the same manner as in Example 20. Br-Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) Br-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n) Br-Ph-Ph-S-CF ₂ -Ph -C ₃ H ₇ (n) Br-Ph-Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) Br-Ph-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n)

In the same manner as in Example 20, the following compound can be synthesized. NC-Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) NC-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n) NC-Ph-Ph-S-CF ₂ -Ph -C ₃ H ₇ (n) NC-Ph-Ph-S-CF ₂ -Ph-C ₅ H ₁₁ (n) NC-Ph-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n)

Example 21 p- (α, α, α-trifluorotoluene) of Example 15
Instead of thiol, p-mercaptobenzoic acid (4-n-propylphenyl) is used, and instead of 4 - chloro-chlorodifluoromethylbenzene, 4 -n- propyl-chlorodifluoromethylbenzene is used. -Difluoro-4-n
-Propylbenzyl-4 '-(4 "-n-propylphenoxycarbonyl) phenylthioether was obtained. (Yield 78%) nC ₃ H ₇ -Ph-OCO-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

[0167]

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The analysis results of this compound are shown below. ^{MS m / e 440 (M +} ) IR 1205cm -1 (CF), 1690cm -1 (C = O)

In the same manner as in Example 21, the following compound can be synthesized. CH ₃ -Ph-OCO-Ph-S-CF ₂ -Ph-C ₃ H ₇ (n) nC ₃ H ₇ -Ph-OCO-Ph-S-CF ₂ -Ph-Ph-C ₃ H ₇ (n) nC ₃ H ₇ -Ph-CH ₂ CH ₂ -Ph-S-CF ₂ -Ph-C ₃ H ₇ (n)

Example 22 A compound synthesized in Examples 1 to 21 (α, α-difluoro-4-n- synthesized in the preceding step of Example 20) was added to 97.5 wt % of a liquid crystal composition “ZLI-1565” manufactured by Merck. Propylbenzyl-4'-bromophenylthioether (22 kinds of compounds) were added in an amount of 2.5 wt%, respectively, and an optically active substance was further added.
Two types of liquid crystal compositions were obtained. A substrate with an ITO electrode having a pair of polyimide alignment films was arranged so that the electrode surfaces face each other, and the periphery was sealed to form an empty cell.

The above liquid crystal composition was injected into the empty cell,
An STNLCD having a twist angle of the liquid crystal of 240 ° was manufactured. A polarizing film was arranged on both surfaces, and a voltage was applied to the electrodes to perform time-division driving. As a result, high-speed response was obtained in each case.

As a comparative example, an example in which R ^1- (A ¹ ) _m -Y ¹ -is an electron donating group and R ^2- (A ⁴ ) _n -Y ² -is an electron withdrawing group. Compound similar to 1 (nC ₃ H ₇ -Ph-O-CF ₂ -Ph-CO-C ₃ H ₇ (n))
Using the same liquid crystal composition containing 2.5 wt% of
D. As a result, the compound of Example 1 of the present invention (n
_{-C 3 H 7 -CO-Ph-} O-CF 2 -Ph-C 3 STNLC using H ₇ a (n)) D
Is, time-division driving characteristics were exhibited.

[0173]

EFFECT OF THE INVENTION The general formula (1) of the present invention: R ^1- (A ¹ ) _m -Y ¹ -A ² -Z-CF ₂ -A ³ -Y ^2- (A ⁴ ) _n -R ² (wherein Wherein R ¹ , R ² , A ^{1 to} A ⁴ , Y ¹ , Y ² , Z, m and n have the same meanings as defined above. The material has a large dielectric anisotropy (Δε) and can improve the driving characteristics when time-division driving is performed.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Miyajima 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Hidemasa Taka 1160 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa (72) Inventor Katsushi Machida 4-16-31 Okada, Samukawa-cho, Koza-gun, Kanagawa Prefecture (56) References JP-A-2-289529 (JP, A) (58) Fields investigated (Int. Cl. ^7, DB name) C09K 19/20 C09K 19/28 C09K 19/30 C09K 19/42 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] (1) R ^1- (A ¹ ) _m -Y ¹ -A ² -Z-CF ₂ -A ³ -Y ^2- (A ⁴ ) _n -R ² (a) R ^1- (A ¹ ) _m -Y ¹ -is an electron-withdrawing group; (b) R ^2- (A ⁴ ) _n -Y ² -is an electron-donating group; (c) A ¹ , A ³ , a ⁴ is independently trans to each other - 1,4 - cyclo <br/> hexylene or 1,4 - a full Eniren group, a ² is 1,4 -
A full Eniren group, A ^1, A ² is one or two or more halogen atoms as a substituent, may have a cyano group, A ^3, one present in the group A ⁴ or 2 More than CH
The group may be substituted by a nitrogen atom, (d) Y ¹ is -OCO-, -CO- or a single bond, and (e) Y ² is -C≡C-, -CH = CH-,- CH ₂ CH _2- , -OCH _2- , -CH ₂ O-
Or (f) Z is an oxygen atom or a sulfur atom, (g) m and n are independently 0 or 1, and (h) R ¹ is one or more hydrogen atoms. An alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, an alkoxy group,
Acyl group or alkoxycarbonyl group, halogen source
A child or a cyano group, the carbon - may also be part of the carbon bond is a double bond, also carbon - may be an oxygen atom is inserted between carbon bonds, (i) R ² is An alkyl group or an alkoxy group having 1 to 10 carbon atoms, a part of the carbon-carbon bond may be a double bond, or an oxygen atom may be inserted between the carbon-carbon bond. A liquid crystal composition comprising a difluoromethylene compound represented by the following formula: The general formula (1): R ^1- (A ¹ ) _m -Y ¹ -A ² -Z-CF ₂ -A ³ -Y ^2- (A ⁴ ) _n -R ² ( b ) R ^2- (a ⁴⁾ _n -Y ² - is an electron donating ^{group, (c ') a 1,} a 3, a 4 is trans independently of one another - 1,4 - shea click <br/> Rohekishiren group or 1,4 - a full Eniren group, a ² is 1,4 has one or two or more halogen atoms or a cyano group as a substituent - an off Eniren group, a ¹ is a substituent It may have one or more halogen atoms or cyano groups, and one or more CH groups present in the groups A ³ and A ⁴ may be substituted with nitrogen atoms. , ( D ) Y ¹ is -OCO-, -CO- or a single bond, ( e ) Y ² is -C≡C-, -CH = CH-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-
Or ( f ) Z is an oxygen atom or a sulfur atom, ( g ) m and n are each independently 0 or 1, and ( h ) R ¹ is one or more hydrogen atoms. An alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, an alkoxy group,
Acyl group or alkoxycarbonyl group, halogen source
A child or a cyano group, the carbon - may also be part of the carbon bond is a double bond, also carbon - may be an oxygen atom is inserted between carbon bonds, (i) R ² is An alkyl group or an alkoxy group having 1 to 10 carbon atoms, and a part of the carbon-carbon bond may be a double bond, or an oxygen atom may be inserted between the carbon-carbon bonds. A liquid crystal composition comprising a difluoromethylene compound represented by the following formula: Wherein Ri Y ¹ is -CO- der, A ² and A ³ are both substituted
A 1,4-phenylene group having no group.
3. The liquid crystal composition according to item 1. 4. A liquid crystal display device, wherein the liquid crystal composition according to claim 1 , 2 or 3 is sandwiched between a pair of substrates provided with electrodes and a voltage is applied to drive the liquid crystal composition in a time division manner.