KR101724588B1 - Bent-core dimesogenic compound and method for preparing thereof - Google Patents

Abstract

More particularly, the present invention relates to a bending-nucleus mesogen compound and a method for producing the same. More particularly, the present invention relates to a bending-nucleus mesogen compound and a method for preparing the same, Compounds and mesogenic compounds having asymmetric bend shape by using an alkyl flexible lattice, and a method for producing the same.
The bending-nucleus mesogen compound of the present invention has a nematic phase felxoelectric property and can exhibit a high-speed response characteristic, and is used as a source material for realizing a ferroelectric liquid crystal display excellent in electric / optical and dynamic characteristics This is possible.

Description

Bent-core dimesogenic compounds and methods for preparing the same,

More particularly, the present invention relates to a bending-nucleus mesogen compound and a method for producing the same. More particularly, the present invention relates to a bending-nucleus mesogen compound and a method for preparing the same, Compounds and mesogenic compounds having asymmetric bend shape by using an alkyl flexible lattice, and a method for producing the same.

Liquid crystal displays with liquid crystal and semiconductor technology are thin, light and low in power consumption. Because of these advantages, liquid crystal displays are leading the large display and TV market as well as computer monitors.

The latest LCD development and production is led by Korea. In particular, Samsung Electronics and LG Display are competing in the global market for the first and second in the world. In order to preoccupy the large-sized LCD market, we are investing a lot of budget and are adding the latest LCD line like the 10th generation line. In particular, this next-generation LCD production technology focuses on the development of large-screen LCD panels for fixed-line and smart TVs to be developed in the future.

In the global TV market, various displays (PDP, OLED, etc.) are in the fiercest competition. LCDs must meet high performance demands in order to lead the TV market. LCDs are rapidly responding to major performance factors that impede entry into the TV market, such as improved response speed, noticeable toughness, securing a wide viewing angle, and improved luminance. In the future, the demand for large-screen, high-definition, and 3D TVs is expected to grow dramatically due to income increase, full-scale digital broadcasting and home theater spreading. However, Speed, and visibility, it does not meet the specifications required for full-HDTV flat panel displays.

(TN) mode, (2) IPS (In-Plane Switching) mode, or FFS (Fringe-Field Switching) mode, which can be divided into four groups according to how the initial nematic liquid crystal images are arranged. Mode, MVA (Multi-domain VA) and PVA (Patterned VA) mode, and OCB (Optically Compensated Bend) mode. As such, in the mass production of LCDs, the liquid crystal mode using the existing nematic phase is utilized, and the characteristics of the liquid crystal itself reaches the limit, so the performance for the next generation 3D LCD is not provided properly.

Flexoelectric or ferroelectric liquid crystals exhibiting macroscopic spontaneous polarization characteristics are one of the liquid crystal molecules that can meet the requirements of the fast response speed required in recent 3D TVs because they can exhibit fast electro-optical response characteristics. In the case of bent-nucleus liquid crystal molecules, it is one of the novel liquid crystal materials capable of having a high-speed response characteristic of several ms or less due to the anisotropy of the molecules themselves and the flexoelectricity characteristic macroscopically when the liquid crystal having such a molecular structure is oriented. The research on the existing flexoelectricity has mainly been focused on maximizing the flexoelectricity using the dopant in the existing nematic liquid crystals. Therefore, the improvement of the response speed that can be obtained was insignificant, the operating temperature range, the orientation characteristic, and the electro-optic effect were also inferior to commercialization.

Korean Patent No. 10-1106528

In order to solve the problems of the prior art as described above, the present invention relates to a mesogenic compound having an asymmetric bend-nucleus form in which a cyclic mono-mesogen compound in which fluorine is substituted at the terminal benzene is connected by an alkyl- And a manufacturing method thereof.

The present invention also provides a ferroelectric liquid crystal display having a nematic phase transition characteristic and exhibiting a high-speed response characteristic, and having excellent electric / optical and dynamic characteristics, which can be used as a source material, And a method for producing the same.

It is another object of the present invention to provide a liquid crystal composition and a liquid crystal display device in which the bending-nucleus comprises a mesogen compound.

In addition, the present invention can produce bentonuclear mesogen compounds which can exhibit different optical properties due to different molecular arrangements under the same voltage, and thus can be applied to an LC mode or an application capable of modulating with a frequency A liquid crystal composition and a liquid crystal display device.

In order to accomplish the above object, the present invention provides a bending-nucleus mesogenic compound represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F, COO, -C = O, -CN = N or -NN, m is an integer of 0 to 1, n is an integer of 3 to 5, and y is an integer of 3 to 12.

In particular, it is preferred that the bending-nucleus mesogenic compound is a compound represented by the following formula (1a) or (1b):

[Formula 1a]

[Chemical Formula 1b]

In the above formula (1a) or (1b)

n is an integer of 5, 6 or 12;

The present invention also relates to a method of producing an Alq3 flexible lattice; Preparing a benzimene compound having five benzenes and having a fluorine-substituted benzene at one end thereof in a bent form; And a step of reacting a benzene compound having five benzene groups and a benzene compound having a fluorine-substituted bicyclic structure at one end thereof with benzene, and a process for preparing the bending-nucleus bi-mesogen compound represented by the above formula .

The alkyl flexible lattice is preferably a compound represented by the following formula (2): < EMI ID =

(2)

n is an integer of 5, 6 or 12;

Wherein the one mesogen compound is 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate or 3- (2,4,6- Carboxy) phenyl 4 [4- (hydroxy) benzoyloxy] benzoate.

The present invention also provides a liquid crystal composition comprising a bending-nucleus mesogen compound represented by the above formula (1). At this time, it is preferable that the bending-nucleus mesogenic compound represented by Formula 1 is a compound represented by Formula 1a or 1b.

The bending-nucleus mesogen compound represented by Formula 1 is preferably contained in the liquid crystal composition in an amount of 1 to 10% by weight.

The present invention also provides a liquid crystal display device including the liquid crystal composition in a liquid crystal layer.

The bending-nucleus mesogen compound according to the present invention exhibits a nematic phase felxoelectric property and can exhibit a high-speed response characteristic, and is a source material for realizing a ferroelectric liquid crystal display having excellent electric / optical and dynamic characteristics. It is possible to use. In addition, the liquid crystal cell produced by using the bent-nucleus mesogen compound produced according to the present invention can exhibit different optical characteristics due to a change in molecular arrangement according to the frequency change under the same voltage, LC mode or application is possible.

1 is a diagram showing DSC thermal analysis results of the compounds of formulas a-1, 1a-2, 1a-3, lb-1, lb-2 and lb-3 prepared according to an embodiment of the present invention.
2 and 3 are diagrams showing mesophase formation periods of the compounds of formulas a-1, 1a-2, 1a-3, 1b-1, 1b-2 and 1b-3 prepared according to an embodiment of the present invention to be.
4 to 9 are schematic cross-sectional views of a compound of Formula a-1, 1a-2, 1a-3, 1b-1, 1b-2 or 1b-3 prepared according to an embodiment of the present invention, Fig.
10 and 11 are graphs showing the results of measurement of the electro-optical properties of the compound of Formula 1a-3 prepared according to one embodiment of the present invention.
12 and 13 are schematic diagrams for observing the behavior of molecules according to voltage intensity and frequency using the compound of Formula 1a-3 prepared according to one embodiment of the present invention.
FIG. 14 is a graph showing the results obtained by applying a voltage of 160 ° C., which is SmX phase, to the compound of formula (1a-3) prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, a cyclic mono-mesogen compound having a fluorine-substituted mesogen group at one end and a mono-isogen compound having an asymmetric bend are connected to each other using an alkyl flexible lattice This mesogenic compound having a bending-nuclear structure was synthesized, and the ferroelectricity in the mesogenic molecule thus synthesized and the nematic phase flexoelectric property exhibited by the bending-nucleus liquid crystal molecule were confirmed. .

Further, it was confirmed that the liquid crystal cell produced by using the bent-nucleus mesogen compound produced according to the present invention can exhibit different optical characteristics due to different molecular arrangement according to the frequency change under the same voltage, Possible application to LC mode or application is possible.

The present invention provides a bending-nucleus mesogenic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F, COO, -C = O, -CN = N or -NN, m is an integer of 0 to 1, n is an integer of 3 to 5, and y is an integer of 3 to 12.

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F More preferably at least 4 F and most preferably X ₂ , X ₃ and X ₄ or X ₁ , X ₃ and X ₅ are F and n is an integer from 5 to 12, 5, 6, or 12, respectively.

That is, the bending-nucleus mesogen compound represented by the above-mentioned formula (1) has a fluorine-substituted mesogen at the 3,4,5- or 2,4,6-position of the terminal benzene and 5, 6 or 12 carbon atoms It is preferred that the bending-nucleus asymmetry with an alkyl flexible lattice having a < RTI ID = 0.0 >

Specifically, the bending-nucleus mesogenic compound represented by Formula 1 is preferably a compound represented by Formula 1a or 1b.

[Formula 1a]

[Chemical Formula 1b]

In the above formula (1a) or (1b)

n is an integer of 5, 6 or 12;

The compound represented by the above formula (1a) or (1b) has five benzenes, mesogen in which fluorine is substituted at the 3,4,5- or 2,4,6-position of one end benzene, and mesogen with an asymmetric structure Is a mesogenic compound having a bend-nucleus asymmetric structure connected by an alkyl flexible lattice.

The bending-nucleus mesogen compound represented by the above formula (1) has an alkyl fluorine-containing lattice and five benzenes, and benzene at one end can be prepared by reacting a cyclic monomethine compound substituted with fluorine.

Specifically, the bending-nucleus mesogens represented by Formula 1 may be prepared by preparing an alkylated flexible lattice according to the following Reaction Scheme 1, preparing 5-benzene, And a step of reacting the alkyl flexible lattice with a mono-isogen compound.

The following Scheme 1 shows an example of the method for preparing the bending-nucleus mesogen compound of the present invention. The following Reaction Scheme 1 is only one example of the process for preparing mesogenic compounds of the present invention. The process of the present invention is not limited to the following Reaction Scheme 1, but may be carried out by various methods Of course.

[Reaction Scheme 1]

In the above Reaction Scheme 1,

X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F, Is at least 4 F, most preferably X ₂ , X ₃ and X ₄ or X ₁ , X ₃ and X ₅ are F,

n is an integer of 5 to 12, more preferably 5, 6 or 12;

Particularly, in the bending-nucleus mesogen compound of the present invention, the cyclic monomethine compound having 5 benzenes in which benzene at one end is substituted with fluorine is 3- (3,4,5-trifluorophenyl (Carboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate or 3- (2,4,6-trifluorophenylcarboxy) phenyl 4 [4- (hydroxy) benzoyloxy] benzoate Do.

Hereinafter, the method for preparing the bending-nucleus mesogenic compound represented by the formula (Ia) or (Ib) of the present invention will be described in more detail in each step.

(1) Preparation of Alkyl Flexible Grids (Scheme 2)

[Reaction Scheme 2]

In the above Reaction Scheme 2, n is 5, 6 or 12.

Referring to Reaction Scheme 2, ethyl 4-hydroxybenzoate, which is a starting material, is dissolved together with K ₂ CO ₃ in a solvent, preferably DMF, and then 1,5-dibromo Dibromohexane, 1,12-dibromododecane, 1,5-dibromopentane, 1,6-dibromohexane, 1,12-dibromododecane, Bis (4-carboxyphenoxy) pentane, 1,6-bis (4-carboxyphenoxy) hexane, ) Or 1,12-bis (4-carboxyphenoxy) dodecane is prepared.

Then, the above prepared 1,5-bis (4-carbethoxyphenoxy) pentane, 1,6-bis (4-carbethoxyphenoxy) hexane (1,12-Bis (4-carbethoxyphenoxy) dodecane) is dissolved in a solvent, and then 1,12-bis (4-carbethoxyphenoxy) (4-carboxyphenoxy) pentane represented by the following formula (2), 1,6-bis (4-carboxyphenoxy) pentane, Bis (4-carboxyphenoxy) dodecane or 1,12-bis (4-carboxyphenoxy) dodecane. At this time, a mixed solvent in which ethanol and distilled water are mixed at a ratio of 1: 1 may be used as the solvent. The reaction can also be terminated by the addition of HCl until the pH of the reaction mixture is equal to 1.

(2)

n is an integer of 5, 6 or 12;

(2) Preparation of 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy]

[Reaction Scheme 3]

In Scheme 3,

X ₂ , X ₃ and X ₄ are F or X ₁ , X ₃ and X ₅ are F.

Referring to Reaction Scheme 3, 3-hydroxybenzaldehyde is reacted with N, N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine , DMAP) and then reacted with 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate (4 ).

The prepared 3-formylphenyl 4- (benzyloxy) benzoate (4) and resorcinol were dissolved in a solvent, specifically, tetrahydrofuran, sodium chlorite and sodium chloride were added to the mixed solution, A solution in which sodium phosphate monobasic monohydrate is dissolved is dropped and reacted to prepare 3-carboxyphenyl 4 (benzyloxy) benzoate (5).

The above 3-carboxyphenyl 4- (benzyloxy) benzoate (5), 3,4,5- or 2,4,6-trifluorophenol (3,4,5- , DCC and DMAP are reacted in a solvent to give 3,4,5- or 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (3,4,5- 4,6-trifluorophenyl 3- [4- (benzyloxy] benzoate) (6) is prepared. Dichloromethane can be used as the solvent.

The above 3,4,5- or 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (6) is dissolved in a solvent, specifically tetrahydrofuran, and 10% Pd C is added to the reaction mixture while hydrogen is being injected to form 3,4,5- or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (3,4,5-or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (7).

After dissolving the 3,4,5- or 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (7), DCC and DMAP in a solvent, 4- 4- (4- (benzyloxy) benzoyloxy) benzyloxy) benzoic acid to give 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (3,4,5-or 2,4,6-trifuorophenyl carboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate] (8).

Subsequently, the 4- (4- (benzyloxy) benzoyloxy) benzoate (8) is dissolved in a solvent, specifically, tetrahydrofuran The reaction was carried out by adding 10% Pd-C in the presence of hydrogen to give 3- (3,4,5- or 2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxyphenyl] Benzoyloxy] benzoate (9).

(3) Preparation of compound of formula (Ia) or compound of formula (Ib) (scheme 4)

[Reaction Scheme 4]

In the above Reaction Scheme 4, X ₂ , X ₃ and X ₄ are F, X ₁ , X ₃ and X ₅ are F, and n is 5, 6 or 12.

The compound represented by the above formula (1a) can be prepared by reacting 1,5-bis (4-carboxyphenoxy) pentane, Bis (4-carboxyphenoxy) hexane or 1,12-bis (4-carboxyphenoxy) dodecane (1,12-Bis -carboxyphenoxy) dodecane) is reacted with SOCl ₂ and pyridine. To the reaction product formed by the reaction, 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate, which is a simple mesogen compound, And then adding the dissolved solution to the solution.

In addition, the compound represented by the above formula (1b) can be produced by reacting the alkyl flexible lattice of 1,5-bis (4-carboxyphenoxy) pentane, 1,6-bis - SOCl ₂ in carboxyphenoxy) hexane (1,6-bis (4-carboxyphenoxy ) hexane) or 1,12-bis (4-carboxyphenoxy) dodecane (1,12-bis (4-carboxyphenoxy ) dodecane) And pyridine are added and reacted. To the reaction product resulting from the reaction is dissolved a solvent, specifically, a methylene chloride compound, 3- (2,4,6-trifluorophenylcarboxy) phenyl 4 [4- (hydroxy) benzoyloxy] benzoate And then reacting the resulting solution.

The present invention also provides a liquid crystal composition comprising the compound represented by the above formula (1).

The liquid crystal composition may include components commonly used in liquid crystal compositions in the art. In particular, in the present invention, a horizontal alignment liquid crystal composition can be prepared by mixing the compound represented by Formula 1a or 1b and a horizontal alignment member.

The compound represented by Formula 1 is contained in the liquid crystal composition in an amount of 1 to 10% by weight, more preferably 1 to 5% by weight, and most preferably 2% by weight. If the content is less than 1% by weight, the effect may be insignificant. If the content is more than 10% by weight, the characteristics of the guest may be more prevalent than the characteristics of the host.

The present invention also provides a liquid crystal display device including the liquid crystal composition in a liquid crystal layer on a substrate.

It is to be understood that the above-described liquid crystal display device can be manufactured by a known method used in the art, and these manufacturing methods do not limit the scope of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are for purposes of illustration only and are not intended to limit the scope of protection of the present invention.

Reagents and Materials

The reagents and solvent catalysts used in Examples and Experimental Examples were prepared by reacting 3-hydroxybenzaldehyde of ACROS-ORGANICS and resorcinol of SIGMA-ALDRICH, sodium chlorite, sodium phosphate monobasic monohydrate, 1,5-dibromopentane, 1,6-dibromohexane, , 12-dibromododecane, 4-benzyloxybenzoic acid, N, N'-dicyclohexylcarbodiimide (DCC) and the ethyl 4-hydroxy benzoate, 3,4,5-Trifluorophenol, 2,4,6-Trifluorophenol, 4-dimethylaminopyridine ), 4-benzyloxybenzoic acid, palladium 10% on canbon (10% Pd-C), JUNSEI's tetrahydrofurane (THF), dichloromethane and Daejung's potassium hydroxide and potassium carbonate. The reagents and solvents used in the purification were purified by using SIGMA-ALDRICH Magnesium sulfate only for the dichloromethane of Daejung Co., and chloroform, methanol, ethanol, hexane, diethyl ether and hydrochloric acid of Daejung Co. were purchased and used without any purification process The size of silica gel used for column chromatography was 0.063 ~ 0.200 mm. The structures of the compounds synthesized by the reaction step were the Scinco NICOLET 6700 FT / IR spectrometer and Biospin 400 Mhz ¹ H NMR of Bruker. In the NMR experiments, chemical shift values were obtained based on the tetramethylsilane (TMS) or the deuterated peptide of the solvent used. Finally, the synthesized compounds were analyzed by using a Flash 2000 element analyzer from ThermoFisher. The calculated carbon and hydrogen composition ratios and measured carbon and hydrogen composition ratios were compared and analyzed. The thermal behavior of the final compounds was investigated using a DSC 200 F3 differential scanning calorimeter of NETZSCH at a heating rate of 10 ° C / min under a nitrogen stream. To observe the optical structure on the liquid crystal, a mettler FP82HT thermocouple Axioskop 40 Pol polarization microscope (POM) from Zeiss was used. The orientation film of the horizontal alignment cell was SE 6514 horizontal alignment film of Nissan.

Example 1. Preparation of Alkyl Flexible Grids

1-1. Preparation of 1,5-bis (4-carbethoxyphenoxy) pentane (1,5-Bis (4-carbethoxyphenoxy) pentane)

(90 mmol) of ethyl 4-hydroxybenzoate were dissolved in DMF, 24.9 g (180 mmol) of K ₂ CO ₃ was added, and the mixture was stirred at room temperature for 30 minutes. 10.3 g (45 mmol) of 1,5-dibromopentane was added dropwise thereto, the temperature was raised to 140 ° C, and the reaction was carried out with stirring for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, re-precipitated in cold distilled water, and filtered. The solid thus obtained was vacuum-dried, and then dissolved in a minimum amount of chloroform. The reaction product was recrystallized by alternating between ethanol and chloroform to obtain a solid product, 1,5-bis (4-carbethoxyphenoxy) pentane.

Yield: 76.8%, (KBr pellet, cm ^-1 ): 3053 (Aromatic CH stretch), 2991, 2952, 2871 (Aliphatic CH stretch), 1716 (Conj. C = O stretch), 1605, 1512 stretch), 1277, 1252, 1171 (CO stretch); ¹ H NMR (400 MHz, Acetone-d ₆ ,? In ppm): 7.97-7.94 (m, 4H, Ar-H), 7.04-7.00 (m, 4H, Ar-H), 4.33-4.27 , OCH), 4.14 (t, J = 6.4 Hz, 4H, OCH 2 CH 3), 1.937-1.867 (m, 4H, OCH 2 CH 2 CH 2 CH 2 CH 2 O), 1.729-1.670 (m, 2H, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O), 1.35-1.29 (m, 6H, OCH ₂ CH ₃ )

1-2. Preparation of 1,6-bis (4-carbethoxyphenoxy) hexane (1,6-Bis (4-carbethoxyphenoxy) hexane)

10.0 g (60 mmol) of ethyl 4-hydroxybenzoate were dissolved in DMF, 8.44 g (60 mmol) of K ₂ CO ₃ was added, and the mixture was stirred at room temperature for 30 minutes. 7.32 g (30 mmol) of 1,6-dibromohexane was added dropwise thereto, the temperature was raised to 140 ° C, and the mixture was reacted with stirring for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, re-precipitated in cold distilled water, and filtered. The solid thus obtained was vacuum-dried and then dissolved in a minimum amount of chloroform. The reaction product was recrystallized by alternating between ethanol and chloroform to obtain a solid product, 1,6-bis (4-carbethoxyphenoxy) hexane.

Yield: 74.8%, (KBr pellet, cm ^-1 ): 3050 (Aromatic CH stretch), 2980, 2941, 2870 (Aliphatic CH stretch), 1710 (Conj. C = O stretch), 1605, 1509 stretch), 1278, 1249, 1172 (CO stretch); ¹ H NMR (400 MHz, Acetone-d ₆ ,? In ppm): 7.97-7.93 (m, 4H, Ar-H), 7.03-7.00 (m, 4H, Ar-H), 4.32-4.27 , OCH), 4.11 (t, J = 8 Hz, 4H, OCH 2 CH 3), 1.89-1.83 (m, 4H, OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O), 1.60-1.56 (m, _{4H, OCH 2 CH 2 CH 2} CH 2 CH 2 CH 2 O), 1.33 (t, J = 8 Hz, 6H, OCH 2 CH 3)

1-3. Preparation of 1,12-bis (4-carbethoxyphenoxy) dodecane (1,12-Bis (4-carbethoxyphenoxy) dodecane)

15.0 g (90 mmol) of ethyl 4-hydroxybenzoate were dissolved in DMF, 16.5 g (12 mmol) of K ₂ CO ₃ was added, and the mixture was stirred at room temperature for 30 minutes. 11.2 g (34 mmol) of 1,12-dibromododecane was added dropwise thereto, the temperature was raised to 140 ° C, and the mixture was reacted with stirring for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, re-precipitated in cold distilled water, and filtered. The solid thus obtained was vacuum-dried and then dissolved in a minimum amount of chloroform. The reaction product was recrystallized by alternating between ethanol and chloroform to obtain a solid product, 1,12-bis (4-carbethoxyphenoxy) dodecane.

Yield: 81.0%, (KBr pellet, ㎝ -1): 3075 (Aromatic CH stretch), 2986, 2937, 2852 (Aliphatic CH stretch), 1715 (. Conj C = O stretch), 1606, 1508 (Aromatic C = C stretch), 1278, 1257, 1168 (CO stretch); ¹ H NMR (400 MHz, Acetone-d ₆ ,? In ppm): 7.97-7.93 (m, 4H, Ar-H), 7.03-7.00 (m, 4H, Ar-H), 4.32-4.27 , OCH), 4.08 (t, J = 8 Hz, 4H, OCH 2 CH 3), 1.83-1.76 (m, 8H, OCH 2 CH 2 CH 2 (CH 2) 6 CH 2 CH 2 CH 2 O), 1.50 _{-1.37 (m, 12H, OCH 2} CH 2 CH 2 (CH 2) 6 CH 2 CH 2 CH 2 O), 1.35-1.29 (m, 6H, OCH 2 CH 3)

1-4. Preparation of 1,5-bis (4-carboxyphenoxy) pentane

13.9 g (34.0 mmol) of 1,5-bis (4-carbethoxyphenoxy) pentane prepared in the above 1-1 was dissolved in a mixed solvent of ethanol and distilled water at a ratio of 1: 1, and then 4.86 g 85.0 mmol) were added and refluxed with stirring at 90 ° C overnight. The reaction was terminated by the addition of hydrochloric acid until the pH reached 1. After completion of the reaction, the reaction mixture was cooled to room temperature and washed with distilled water until the pH became neutral with excess water and filtered. The solid thus obtained was washed with ethanol and chloroform, and vacuum dried to obtain 1,5-bis (4-carboxyphenoxy) pentane as a white solid product.

Yield: 91.7%, (KBr pellet, cm ^-1 ): 3347-2170 (OH stretch), 3075 (Aromatic CH stretch), 2986, 2937, 2852 (Aliphatic CH stretch), 1694 1603, 1514 (Aromatic C = C stretch), 1319, 1294, 1257, 1172 (CO stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 7.88-7.85 (m, 4H, Ar-H), 7.02-6.98 (m, 4H, Ar-H), 4.06 (t, J = 6 Hz, 4H, OCH), 1.83-1.76 (m, 4H, OCH 2 CH 2 CH 2 CH 2 CH 2 O), 1.60-1.55 (m, 2H, OCH 2 CH 2 CH 2 CH 2 CH 2 O)

1-5. Preparation of 1,6-bis (4-carboxyphenoxy) hexane

9.3 g (22.0 mmol) of 1,5-bis (4-carbethoxyphenoxy) hexane prepared in 1-2 above was dissolved in a mixed solvent of ethanol and distilled water at a ratio of 1: 1, and then 3.02 g of KOH 53.0 mmol) were added thereto, and the mixture was refluxed at 90 ° C with stirring overnight. The reaction was terminated by the addition of hydrochloric acid until the pH reached 1. After completion of the reaction, the reaction mixture was cooled to room temperature and washed with distilled water until the pH became neutral with excess water and filtered. The solid thus obtained was wiped with ethanol and chloroform, and vacuum dried to obtain 1,6-bis (4-carboxyphenoxy) hexane as a white solid product.

Yield: 89%, (KBr pellet, cm ^-1 ): 3347-2170 (OH stretch), 3050 (Aromatic CH stretch), 2946, 2916, 2874 (Aliphatic CH stretch), 1694 1603, 1514 (Aromatic C = C stretch), 1319, 1294, 1257, 1172 (CO stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 7.86 (d, J = 8 Hz, 4H, Ar-H), 6.99 (d, J = 8 Hz, 4H, Ar-H), 4.03 (t, J = 12 Hz, 4H, OCH), 1.74 (d, J = 8 Hz, 4H, OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O), 1.47 (s, 4H, OCH 2 CH 2 CH ₂ CH ₂ CH ₂ CH ₂ O)

1-6. Preparation of 1,12-bis (4-carboxyphenoxy) dodecane (1,12-Bis (4-carboxyphenoxy) dodecane)

13.7 g (27.0 mmol) of 1,12-bis (4-carbethoxyphenoxy) dodecane prepared in 1-3 above was dissolved in a mixed solvent of ethanol and distilled water at a ratio of 1: 1, followed by the addition of 3.86 g (68.0 mmol) were added, and the mixture was refluxed at 90 ° C with stirring overnight. The reaction was terminated by the addition of hydrochloric acid until the pH reached 1. After completion of the reaction, the reaction mixture was cooled to room temperature and washed with distilled water until the pH became neutral with excess water and filtered. The solid thus obtained was wiped with ethanol and chloroform, and vacuum dried to obtain 1,12-bis (4-carboxyphenoxy) dodecane as a white solid product.

Yield: 89.9%, (KBr pellet, cm ^-1 ): 3295-2346 (OH stretch), 3063 (Aromatic CH stretch), 2940, 2933, 2861 (Aliphatic CH stretch), 1683 1607, 1514 (Aromatic C = C stretch), 1296, 1255, 1168 (CO stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 7.88-7.84 (m, 4H, Ar-H), 7.00-7.97 (m, 4H, Ar-H), 4.01 (t, J = 6 Hz, 4H, OCH), 1.74-1.67 (m, 4H, OCH 2 CH 2 CH 2 (CH 2) 6 CH 2 CH 2 CH 2 O), 1.38 (d, J = 8 Hz, 4H, OCH 2 CH 2 _{CH 2 (CH 2) 6 CH} 2 CH 2 CH 2 O), 1.26 (s, 12H, OCH 2 CH 2 CH 2 (CH 2) 6 CH 2 CH 2 CH 2 O)

Example 2. 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate Synthesis

2-1. Preparation of 3-formylphenyl 4- (benzyloxy) benzoate (3-formylphenyl 4- (benzyloxy) benzoate)

(65.7 mmol) of 4- (benzyloxy) benzoic acid and 0.80 g (6.57 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in MC Followed by stirring in a nitrogen atmosphere for 30 minutes. Thereafter, 16.3 g (78.8 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) was added and stirred under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the resulting urea was filtered off with filter paper, washed three times with aqueous NaCl solution and distilled water, and then subjected to vacuum distillation and column chromatography using a single solvent of dichloromethane as a developing solvent. The resulting solution was distilled under reduced pressure and vacuum dried to obtain a white solid product, 3-formylphenyl 4- (benzyloxy) benzoate.

Yield: 86.2%, (KBr pellet, cm ^-1 ): 3060 (Aromatic CH stretch), 2925, 2854, 2816 (Aliphatic CH stretch), 2741 (CH aldehyde), 1720 1507 (Aromatic C = C stretch), 1276, 1223, 1170 (CO stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 10.093 (s, 1H, Ar-CHO), 8.17 (d, J = 8 Hz, 2H, Ar-H), 7.88 (d, J = 1H, Ar-H), 7.82 (d, J = 4 Hz, 1H, Ar-H), 7.72 (t, J = 8 Hz, 1H, Ar-H), 7.638-7.630 H, Ar-H), 7.618-7.516 (m, 2H, Ar-H), 7.40 (t, J = 12 Hz, 3H, Ar- 5.29 (s, 2H, OCH3)

2-2. Preparation of 3-carboxyphenyl 4- (benzyloxy) benzoate (3-carboxyphenyl 4- (benzyloxy) benzoate)

18.7 g (56.4 mmol) of the obtained 3-formylphenyl 4- (benzyloxy) benzoate and 6.95 g (63.2 mmol) of resorcinol were dissolved in tetrahydrofuran. A solution prepared by dissolving 30.6 g (33.8 mmol) of sodium chlorite and 20.3 g (169 mmol) of sodium phosphate monohydrate in distilled water was added dropwise, and the mixture was stirred for 24 hours under a nitrogen atmosphere. After completion of the reaction, the THF was distilled off under reduced pressure, and then precipitated in distilled water. Then, hydrochloric acid was added until the pH of the reactant became 1, and then the reaction solution was washed with distilled water and filtered until the pH became neutral with excess water. Subsequently, the organic layer was dried in vacuo and recrystallized from ethanol to obtain a white solid product, 3-carboxyphenyl 4- (benzyloxy) benzoate.

Yield: 86.2%, (KBr pellet, cm ^-1 ): 3448-2345 (OH stretch), 3066 (Aromatic CH stretch), 2970, 2884, 2830 (Aliphatic CH stretch), 1720 1610, 1513 (Aromatic C = C stretch), 1306, 1263, 1207, 1170 (CO stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 7.91 (t, J = 2 Hz, 2H, Ar-H), 7.61 (d, 1H, J = 8 Hz, Ar-H), 7.58 (s, 1H, Ar-H), 7.50-7.54 (m, 1H, Ar-H), 7.54-7.52 2H, Ar-H), 5.28 (s, 2H, OCH3), 7.39 (t, J = 10 Hz,

2-3. Preparation of 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate

9.54 g (28.7 mmol) of the obtained 3-carboxyphenyl 4- (benzyloxy) benzoate, 5.10 g (34.4 mmol) of 3,4,5-trifluorophenol and 0.35 g (28.7 mmol) of DMAP were dissolved in MC And the mixture was stirred under a nitrogen atmosphere for 30 minutes. 7.10 g (34.4 mmol) of DCC was added thereto, and the mixture was stirred under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the urea produced was filtered off with a filter paper, washed three times with an aqueous solution of NaCl and distilled water, and then subjected to vacuum distillation and column chromatography using a single solvent of dichloromethane as a developing solvent. The solution thus obtained was distilled under reduced pressure and vacuum dried to obtain 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate as a white solid.

Yield: 94.0%, (KBr pellet, ㎝ -1): 3067 (Aromatic CH stretch), 2948, 2896 (Aliphatic CH stretch), 1727 (. Conj C = O stretch), 1605, 1530 (Aromatic C = C stretch) , 1243, 1231, 1169 (CO, CF stretch); ¹ H NMR (400 MHz, CDCl ₃ ,? In ppm): 8.17-8.13 (m, 2H, Ar-H), 8.06-8.03 H), 7.56 (t, J = 8 Hz, 1H, Ar-H), 7.52-7.51 (m, 1H, Ar-H), 7.50-7.32 2H, Ar-H), 6.95-6.90 (m, 2H, Ar-H), 5.18

2-4. Preparation of 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3- [4- (hydroxy) benzoyloxy] benzoate

12.8 g (26.8 mmol) of the 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate obtained above was dissolved in THF. 2.85 g (2.68 mmol) of 10% Pd / C was added and stirred for 30 minutes. Then, hydrogen was directly added to the solution while refluxing at 60 ° C, and the mixture was stirred for 8 hours. After completion of the reaction, the filtrate was distilled under reduced pressure on a filter paper, and hexane was added to the resulting liquid to precipitate the precipitate. The precipitate was then vacuum dried to obtain a white solid product, 3,4,5-trifluorophenyl 3 - [(4- ) ≪ / RTI > benzoyloxy] benzoate.

Yield: 99%, KBr pellet, cm ^-1 : 3434 (OH stretch), 3077 (Aromatic CH stretch), 1738 (Conj. C = O stretch), 1607, 1525 (Aromatic C = C stretch) 1208, 1186, 1162 (CO, CF stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 8.15-8.00 (m, 4H, Ar-H), 7.73-7.64 (m, 2H, Ar-H), 7.39-7.41 (m, 2H , Ar-H), 7.04-7.01 (m, 2H, Ar-H)

2.5. 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzyloxy) benzoyloxy] benzoate

(26.9 mmol) of 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate, 7.36 g (32.2 mmol) of 4- (benzyloxy) g (2.69 mmol) was dissolved in MC and stirred in a nitrogen atmosphere for 30 minutes. Then, 6.65 g (32.2 mmol) of DCC was added and the mixture was stirred under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the urea produced was filtered off the filter paper, washed with NaCl aqueous solution and distilled water three times, distilled under reduced pressure, and subjected to column chromatography using a single solvent of dichloromethane as a developing solvent. The solution thus obtained was distilled under reduced pressure and vacuum dried to obtain 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate as a white solid product.

Yield: 92.8%, (KBr pellet, cm ^-1 ): 3073 (Aromatic CH stretch), 2925, 2878 (Aliphatic CH stretch), 1725 (Conj. C = O stretch), 1607, 1522 , 1275, 1252, 1163 (CO, CF stretch); ^{1 H NMR (400 MHz, CDCl} 3, δ in ppm): 8.29-8.25 (m, 2H, Ar-H), 8.17-8.14 (m, 2H, Ar-H), 8.08-8.06 (m, 1H, Ar 1H, Ar-H), 8.01 (t, J = 2 Hz, 1 H, Ar-H), 7.59 (t, J = 8 Hz, 1H, Ar-H), 7.55-7.52 -7.34 (m, 7H, Ar- H), 7.08-7.05 (m, 2H, Ar-H), 6.95-6.92 (m, 2H, Ar-H), 5.16 (s, 2H, O-CH 2 -H )

2-6. 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- [4-hydroxybenzoyloxy] benzoate 3- (3,4,5-Trifluorophenylcarboxy) phenyl 4- [4- ) benzoyloxy] benzoate

14.9 g (25.0 mmol) of the obtained 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in THF. 2.65 g (2.50 mmol) of 10% Pd / C was added thereto, and the mixture was stirred for 30 minutes, and then hydrogen was directly added to the solution while refluxing at 60 ° C, followed by stirring for 8 hours. After completion of the reaction, the filtrate was distilled under reduced pressure on a filter paper, and then vacuum-dried to obtain a white solid product, 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4-hydroxybenzoyloxy] benzoate ≪ / RTI >

Yield: 95%, (KBr pellet, cm ^-1 ): 3399 (OH stretch), 3080 (Aromatic CH stretch), 1736 (Conj. C = O stretch), 1606, 1528 1216, 1165 (CO, CF stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 10.626 (s, 1H, OH), 8.25 (d, J = 8 Hz, 2H, Ar-H), 8.08-8.01 (m, 4H, ArH), 7.77-7.72 (m, 2H, Ar-H), 7.58-7.50

Example 3. Preparation of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate

3-1. Preparation of 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate

23.9 g (68.6 mmol) of 3-carboxyphenyl 4- (benzyloxy) benzoate obtained in Example 2-2, 12.2 g (82.3 mmol) of 2,4,6-trifluorophenol and 0.84 g mmol) were dissolved in MC and stirred in a nitrogen atmosphere for 30 minutes. 17.0 g (82.5 mmol) of DCC was added thereto, and the mixture was stirred under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the urea produced was filtered off with a filter paper, washed three times with an aqueous solution of NaCl and distilled water, and then subjected to vacuum distillation and column chromatography using a single solvent of dichloromethane as a developing solvent. The solution thus obtained was distilled under reduced pressure and vacuum dried to obtain 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate as a white solid.

Yield: 94.0%, (KBr pellet, cm ^-1 ): 3081 (Aromatic CH stretch), 2946, 2895 (Aliphatic CH stretch), 1728 (Conj. C = O stretch), 1604, 1518 , 1250, 1210, 1169 (CO, CF stretch); ¹ H NMR (400 MHz, CDCl ₃ ,? In ppm): 8.17-8.14 (m, 2H, Ar-H), 8.11-8.09 (M, 2H, Ar-H), 7.60-7.51 (m, 2H, Ar-H), 7.50-7.32 m, 2H, Ar-H) , 5.18 (s, 2H, O-CH 2 -H)

3-2. Preparation of 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3- [4- (hydroxy) benzoyloxy] benzoate

12.8 g (26.8 mmol) of the obtained 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in THF. 2.85 g (2.68 mmol) of 10% Pd / C was added and stirred for 30 minutes. Then, hydrogen was directly added to the solution while refluxing at 60 ° C, and the mixture was stirred for 8 hours. After completion of the reaction, the filtrate was distilled under reduced pressure on a filter paper, and hexane was added to the obtained liquid phase to precipitate the precipitate. The precipitate was then vacuum dried to obtain a white solid product, 2,4,6-trifluorophenyl 3 - [(4- ) ≪ / RTI > benzoyloxy] benzoate.

Yield: 99.4%, KBr pellet, cm ^-1 : 3534 (OH stretch), 3070 (Aromatic CH stretch), 1754 (Conj. C = O stretch), 1609, 1509 (Aromatic C = C stretch) 1258, 1212, 1165 (CO, CF stretch); ^{1 H NMR (400 MHz, Acetone} -d 6, δ in ppm): 9.47 (S, 1H, OH), 8.16-8.08 (m, 4H, Ar-H), 7.77-7.70 (m, 2H, Ar-H ), 7.25-7.18 (m, 2H, Ar-H), 7.04-7.00 (m, 2H,

3.3. 3- (3,4,6-Trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate 3- (3,4,5- benzyloxy) benzoyloxy] benzoate

23.6 g (60.7 mmol) of the obtained 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate, 16.6 g (72.7 mmol) of 4- (benzyloxy) g (6.07 mmol) was dissolved in MC and stirred in a nitrogen atmosphere for 30 minutes. Then, 15.0 g (72.7 mmol) of DCC was added and the mixture was stirred under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the urea produced was filtered off the filter paper, washed with NaCl aqueous solution and distilled water three times, distilled under reduced pressure, and subjected to column chromatography using a single solvent of dichloromethane as a developing solvent. The resulting solution was distilled under reduced pressure and vacuum dried to obtain 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate as a white solid product.

Yield: 96.5%, (KBr pellet, cm ^-1 ): 3082 (Aromatic CH stretch), 2956, 2927 (Aliphatic CH stretch), 1734 (Conj. C = O stretch), 1604, 1510 , 1258, 1211, 1163 (CO, CF stretch); ^{1 H NMR (400 MHz, CDCl} 3, δ in ppm): 8.29-8.26 (m, 2H, Ar-H), 8.16-8.11 (m, 3H, Ar-H), 8.06 (t, J = 2 Hz, 1H, Ar-H), 7.62-7.55 (m, 2H, Ar-H), 7.53-7.33 (m, 7H, Ar-H), 7.08-7.04 m, 2H, Ar-H) , 5.16 (s, 2H, O-CH 2 -H)

3-4. (2,4,6-trifluorophenyl carboxy) phenyl 4- [4- (hydroxyphenyl) carboxy] phenyl 4- [4- ) benzoyloxy] benzoate

3- (2,4,6-trifluorophenyl carboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate (35.1 g, 58.6 mmol) is dissolved in THF. 10% Pd / C (6.24 g, 5.86 mmol) was added thereto, and the mixture was stirred for 30 minutes. After reflux at 60 ° C, hydrogen was directly added to the solution and stirred for 8 hours. After completion of the reaction, the solution filtered through filter paper was distilled under reduced pressure and then vacuum-dried to obtain a white solid product.

35.1 g (58.6 mmol) of the obtained 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate was dissolved in THF. 6.24 g (5.86 mmol) of 10% Pd / C was added thereto, and the mixture was stirred for 30 minutes. Then, hydrogen was directly added to the solution while refluxing at 60 DEG C, and the mixture was stirred for 8 hours. After completion of the reaction, the filtrate was distilled under reduced pressure on a filter paper, and then vacuum-dried to obtain a white solid product, 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4-hydroxybenzoyloxy] benzoate ≪ / RTI >

Yield: 96.7%, KBr pellet, cm ^-1 ): 3534 (OH stretch), 3068 (Aromatic CH stretch), 1743 (Conj. C = O stretch), 1613, 1509 (Aromatic C = C stretch) 1219, 1166 (CO, CF stretch); ^{1 H NMR (400 MHz, DMSO} -d 6, δ in ppm): 10.6 (s, 1H, OH), 8.27-8.24 (m, 2H, Ar-H), 8.15-8.12 (m, 2H, Ar-H ), 8.03-8.01 (m, 2H, Ar-H), 7.83-7.81 (m, 2H, Ar-H), 7.79-7.51 -H)

Example 4. Preparation of the compound of formula (1a-1)

After 0.81 g (2.36 mmol) of 1,5-bis (4-carboxyphenoxy) pentane prepared in Example 1-4 was added to 24 ml of SOCl ₂ at room temperature, one or two drops of pyridine were added, , And the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.90 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 49.7%, (KBr pellet, ㎝ -1): 3076 (Aromatic CH stretch), 2945, 2864 (Aliphatic CH stretch), 1738 (. Conj C = O stretch), 1602, 1525 (Aromatic C = C stretch) , 1253, 1204, 1158 (CO, CF stretch)

Example 5. Preparation of the compound of formula (1a-2)

0.85 g (2.36 mmol) of 1,6-bis (4-carboxyphenoxy) hexane prepared in Example 1-5 was added to 24 ml of SOCl ₂ at room temperature, and one or two drops of pyridine were added thereto. , And the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.90 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 48.0%, (KBr pellet, ㎝ -1): 3076 (Aromatic CH stretch), 2948, 2871 (Aliphatic CH stretch), 1736 (. Conj C = O stretch), 1603, 1529 (Aromatic C = C stretch) , 1254, 1206, 1160 (CO, CF stretch)

Example 6. Preparation of the compound of formula (1a-3)

1.05 g (2.36 mmol) of 1,12-bis (4-carboxyphenoxy) dodecane prepared in Example 1-6 was added to 24 ml of SOCl ₂ at room temperature, followed by adding one or two drops of pyridine, To completely dissolve, and the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.90 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 62.9%, (KBr pellet, cm ^-1 ): 3076 (Aromatic CH stretch), 2919, 2853 (Aliphatic CH stretch), 1737 (Conj. C = O stretch), 1603, 1527 , 1254, 1205, 1160 (CO, CF stretch)

Example 7. Preparation of compound of formula (Ib-1)

After 0.81 g (2.36 mmol) of 1,5-bis (4-carboxyphenoxy) pentane prepared in Example 1-4 was added to 24 ml of SOCl ₂ at room temperature, one or two drops of pyridine were added, , And the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.90 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 20.0%, (KBr pellet, ㎝ -1): 3084 (Aromatic CH stretch), 2941, 2869 (Aliphatic CH stretch), 1743 (. Conj C = O stretch), 1602, 1512 (Aromatic C = C stretch) , 1256, 1205, 1158 (CO, CF stretch)

Example 8. Preparation of the compound of formula (Ib-2)

0.85 g (2.36 mmol) of 1,6-bis (4-carboxyphenoxy) hexane prepared in Example 1-5 was added to 24 ml of SOCl ₂ at room temperature, and one or two drops of pyridine were added thereto. , And the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.90 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 31.5%, (KBr pellet, cm ^-1 ): 3080 (Aromatic CH stretch), 2934, 2873 (Aliphatic CH stretch), 1728 (Conj. C = O stretch), 1604, 1511 , 1254, 1207, 1159 (CO, CF stretch)

Example 9. Preparation of the compound of formula (Ib-3)

1.05 g (2.36 mmol) of 1,12-bis (4-carboxyphenoxy) dodecane prepared in Example 1-6 was added to 24 ml of SOCl ₂ at room temperature, followed by adding one or two drops of pyridine, To completely dissolve, and the mixture was stirred for 4 hours while refluxing. After the reaction was completed, the reaction mixture was cooled to room temperature, and the remaining SOCl ₂ was distilled off under reduced pressure and purified by washing with petroleum ether. A small amount of MC was then added to the purified product and dissolved. To this was added 1 mL each of 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate (3.00 g, 5.72 mmol) dissolved in MC and pyridine , And the mixture was stirred under a nitrogen atmosphere for 72 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and the residue was washed with distilled water, acetone, DMF, and acetone, followed by filtration to obtain a white solid product.

Yield: 60.9%, (KBr pellet, cm ^-1 ): 3077 (Aromatic CH stretch), 2918, 2853 (Aliphatic CH stretch), 1738 (Conj. C = O stretch), 1603, 1510 , 1254, 1206, 1159 (CO, CF stretch)

Experimental Example 1. Identification of chemical structure

FT-IR spectroscopy was used to determine the chemical structures of the compounds of Formulas 1a-1, 1a-2, 1a-3, 1b-1, 1b-2 and 1b-3 prepared in Examples 4 to 9 , And element analysis was carried out, and it is shown in Table 1 below.

If the final product of the compound 1a-1 prepared in Example 4 was shown in the IR spectrum of the two OH respectively 3347 ~ 2170㎝ ^{-1 -1} 3399㎝ and wide absorption band of the reactant in the final reaction step, the end product In the spectrum of the phosphorus compound 1a-1, the absorption band of the OH functional group disappeared. Absorption band due to stretching vibration of aromatic CH at 3076 cm ^-1 , absorption band due to stretching vibration of aliphatic CH at 2945 cm ^-1 and 2864 cm ^-1 , stretching of aromatic C = C at 1602 cm ^-1 and 1525 cm ^-1 in the absorption band due to vibration, and 1253㎝ ^-1, 1204㎝ ^-1 and 1158㎝ ^-1 showed an absorption band due to stretching vibration of CO, CF. And the carbonyl functional group C = O formed by the esterification reaction showed an absorption band at 1738 cm ^-1 . The measured values of the calculated values of C and H through the elemental analysis showed a small error range of + 0.10% and + 0.57%, respectively. From these results, it was confirmed that the desired final product, compound 1a-1, was synthesized, and the compounds 1a-2, 1a-3, 1b-1, 1b-2 and 1b-3 were also synthesized by the same method.

Experimental Example 2: Thermoelectric conversion behavior

DSC thermograms of the compounds of formulas 1a-1, 1a-2, 1a-3, 1b-1, 1b-2 and 1b-3 prepared in Examples 4 to 9 are shown in FIG. 1, The results are shown in FIG. 2 and FIG. 3. The melting point transition temperature and isotropic liquidus transition temperature, melting enthalpy and isotropy enthalpy obtained in the heating and cooling of the final compound on DSC are shown in Table 2 below.

Showed two endothermic peaks during the primary heating, as shown in thermal analysis of the compound of formula 1a-1 prepared in the above formula (4) is also a result, the Figure 1a, this time a large endothermic peak shown in 198.7 ℃ the sample is melting T _m And the endothermic peak at 228.6 ° C corresponds to the T _i transitioning from the liquid crystal phase to the isotropic liquid. During cooling, two exothermic peaks were observed at crystallization and transition from isotropic liquid to meso phase at 143.9 ℃ and 227.2 ℃, respectively. During the second heating, T _m and T _i were observed at 197.1 ° C and 229.9 ° C, respectively.

The results of the thermal analysis of the compound of formula (1a-2) prepared in the above formula (5) showed T _m at 191.9 ° C and T _i at 152.4 ° C in the first heating as shown in FIG. During cooling, endothermic peaks corresponding to crystallization and transition from an isotropic liquid to a mesophase appeared at 151.9 ° C and 255.1 ° C, respectively. At the second heating, a large endothermic peak T _m at 189.7 ° C and a T _i transitioning to an isotropic liquid at 258.5 ° C appeared.

The results of the thermal analysis of the compound of formula (1a-3) prepared in the above formula (6) show that the small endothermic peak at 119.6 ° C. shows the transition between solid and solid, and the large endothermic peak at 210.3 ° C. Melting was equivalent to T _m and the endothermic peak at 173.2 ℃ corresponded to meso phase transition. The endothermic peak at 206.0 ° C corresponds to the T _i transitioning to an isotropic liquid on the meso. During cooling, the T _i transitioning from the isotropic liquid to the meso phase was observed at 207.4 ° C. At cooling, no transition peak appeared between the meso phase and crystallization occurred at 91.1 ° C. At the second heating, two endothermic peaks were observed, corresponding to T _m and T _i at 140.2 ° C and 152.4 ° C, respectively.

The results of the thermal analysis of the compound of formula (Ib-1) prepared in the above formula (7) showed two endothermic peaks at the first heating and an endothermic peak at 173.1 ° C as the solid- denotes a transition, the endothermic peak shown in 198.0 ℃ was equivalent to the crystal melting T _m. In the case of compound 1b-1, there was no endothermic peak corresponding to T _i transitioning to an isotropic liquid on the meso phase. There was no exothermic peak that transitioned from the isotropic liquid to the meso phase during cooling, and only an exotherm peak corresponding to crystallization at 160.8 ° C was exhibited. At the second heating, only the endothermic peak corresponding to T _m was found at 197.8 ° C.

As the thermal analysis of the compound of formula 1b-2 prepared in the above formula (8) is also the result is shown in Figure 1e, at 204.5 ℃ during the first heating showed a large endothermic peak corresponding to T _m, corresponding to a T _i No endothermic peak appeared. However, when cooled, the exothermic peak corresponding to the transition from the isotropic liquid to the mesophase appeared at 223.9 ° C., and at 113.8 ° C., the exotherm peak corresponding to crystallization appeared. During the second heating there was born this ℃ 142.0 and 159.5 ℃ crystal melting T _m appears across unlike when the primary heating, showed an endothermic peak for transition to the isotropic liquid on a meso from 227.9 ℃.

As shown in FIG. 1F, the endothermic peaks at 125.9 ° C and 159.8 ° C were found to be solid - a transition between the solid, the endothermic peak shown in the 179.7 ℃ is was not observed T _i for determining the T _m corresponds to the melting and transition to the isotropic liquid. However, when cooled, an exothermic peak transitioning from an isotropic liquid to a mesophase was observed at 159.3 ° C, and an exotherm peak corresponding to crystallization appeared at 116.7 ° C. At the second heating, two endothermic peaks were observed. The endothermic peak at 131 ° C corresponds to a solid-solid transition, and at 154.8 ° C, an exotherm peak corresponding to T _m appeared.

In addition, 3,4,5-forming temperature intervals on the method of the fluorine-substituted compound (ΔT≡T _i -T _m) to the position of the phenyl group, as shown in Figure 2 when the secondary heating in order to minimize the thermal effect ( 2a). The compounds 1a-1, 1a-2 and 1a-3 exhibited 33 ° C, 66 ° C and 70 ° C, respectively, and when the central carbon number was 5 due to the odd-even effect, , The temperature range of meso phase formation was shorter than that of 6 or 12 due to the arrangement of molecules. In the case of even number of molecules, the longer the alkyl chain was, the more advantageous the molecular arrangement was, there was. Similar to the case of cooling (Fig. 2a), the formation temperature ranges of the mesophase phases of the compounds 1a-1, 1a-2 and 1a-3 were also the same at 83 ° C, 103 ° C and 116 ° C, respectively.

As shown in FIG. 3, the formation temperature range (? T? T _i -T _m ) of the mesophase phase of the fluorine-substituted compound in the 2,4,6-position of the phenyl group is also similarly 3a). In the case of compounds 1b-1, 1b-2 and 1b-3, meso phase could not be formed. In the case of compound 1b-3, the stable temperature range of the mesophase was 65 ° C. When the position of the fluorine substituent was 2,4,6-, the position of the polar group was found to be more disadvantageous to the formation of the meso phase than that of 3,4,5-. Compound 1b-2 and 1b-3 formed a meso phase upon cooling, but did not form a meso phase with compound 1b-3.

Experimental Example 3. Polarizing Microscope Observation

Based on the transition temperature determined by DSC, the temperature dependence of the compounds of the formulas 1a-1, 1a-2, 1a-3, 1b-1, 1b-2 and 1b-3 prepared in Examples 4 to 9 in the polarizing microscope Phase transitions were observed. The heating and cooling rates were measured at 10 ° C / min under the same conditions as DSC, and the observed optical structures of each compound are shown in FIGS. 4 to 9.

FIG. 4 shows a nematic phase observed during cooling after heating up to the isotropic region of the compound 1a-1 prepared in Example 4, as shown in FIGS. 4b and 4c, and FIG. 4d The same nematic phase was observed at the second heating after cooling. FIG. 5 shows a nematic phase as shown in FIG. 5B and FIG. 5C in the same manner as in the case of the compound 1a-1 except that the compound 1a-2 prepared in Example 5 was heated to an isotropic region and then cooled . Also, a nematic phase can be observed as shown in Fig. 5D even during the second heating. Fig. 5 shows the results of the observation of the compound 1a-3 prepared in Example 5 at the time of the first heating and cooling. As shown in Fig. 5a, , And a phase which appeared to be a SmX phase was observed in FIG. 5B. In FIG. 5B, a phase which appeared to be a nematic phase was observed at around 187 ° C. Also, at the time of cooling, only one nematic phase was observed as shown in Figs. 5C and 5D, unlike the case of the first heating.

7 shows the phase observed during the first heating and cooling of compound 1b-1 prepared in Example 7, and Compound 1b-1 does not form a liquid crystal phase during heating and cooling as in the result of DSC As shown in FIG. 7A, it was confirmed that the crystal transitioned to an isotropic liquid at about 197 ° C. as shown in FIG. In addition, it was confirmed that crystallization occurs at about 160 ° C even without cooling to liquid crystal from an isotropic liquid. FIG. 8 shows the phase observed during the first heating and cooling of the compound 1b-2 prepared in Example 8, and only the endothermic peak corresponding to T _m was observed in the DSC results in the first heating 8a and 8b, respectively, which appear to be nematic phases with high fluidity in a polarizing microscope. This is thought to be due to the fact that T _m , which shows a large endothermic peak at the first heating, overlaps with T _i . In cooling, a nematic phase with high fluidity was observed as in DSC results. Figure 9 is the embodiment of the compound prepared in nine primary heating of 1b-3, as shown to the one observed when the second heating during cooling, Fig. 9a during the primary heating, just as T _i does not appear in the DSC Results And 9b, it was observed that the crystal was transferred to an isotropic liquid at the same time as the liquid crystal phase was not observed. 9C, a nematic phase can be observed at the time of cooling, and in FIG. 9D, it can be confirmed that crystallization is different from that shown in FIG. 9D. As a result, the endothermic peaks of large and small were indirectly explained in the DSC results at the first heating and the second heating. As in the case of the first heating, a liquid crystal phase could not be formed even during the second heating. The melting temperatures of the domains were different from each other due to the different types of crystals formed at the time of cooling, as shown in FIGS. 9E and 9F.

Experimental Example 4: Electrical / Optical Properties

The electrical / optical properties of the compound of Formula 1a-3 prepared in Example 9 were measured. The liquid crystal cell was fabricated by coating polyimide as an alignment film on a glass substrate coated with ITO and then rubbing for alignment. Then, two glass substrates rubbed together were bonded in parallel to each other. At this time, the thickness of the cell gap was made 7 μm, and the liquid crystal injection was performed using the capillary effect in an isotropic liquid state.

FIG. 10 shows images observed after application of a voltage and after removal of a voltage. FIG. 10 shows the observation of the cell structure oriented in the rubbing direction at 200 ° C., in which light polarized uniformly in the rubbing direction, I could not see it coming out. In this state, when 6.5 Vm < ^-1 > of 5 Hz is applied, it can be confirmed through FIG. 10B that the polarized light comes out through the analyzer. This was predicted by the switching of the molecules due to the voltage due to the dielectric anisotropy of the liquid crystal due to the applied voltage. Then, when the applied voltage is removed, a black portion where light does not pass through the analyzer and a green portion passing through the analyzer exist as a domain as shown in FIG. 10C. In addition, it was confirmed that there is a light red domain in the green part. This is because in the black region where light does not pass, the bent portion of each mesogen is directed upward or downward on the oriented glass substrate, and the green portion is the counter-clockwise direction of the bent portion of the molecule Thought. Referring to FIG. 10D, it can be seen that when the analyzer is rotated by 10 ° counterclockwise, the black region and the green region change to a light red color, and the light red region becomes green. This was thought to be the direction opposite to the green area where the bendy structure of the light red region before rotating the analyzer. When the analyzer was rotated clockwise by 10 °, the black areas and the green areas became more dark green and the light red areas became more red. However, it can be seen from FIG. 11 that these domains disappear with time.

In addition, the compound 1a-3 has different molecular behavior depending on the intensity and the frequency of the voltage, and a simple schematic diagram thereof is shown in FIG. 12 and FIG.

FIG. 12A shows that when a voltage is applied to a cell at an AC voltage of 15 Vm ^-1 at 1 Hz under a condition of 200 ° C, molecules are moved in a direction perpendicular to the alignment film in a direction parallel to the direction of the electric field when a voltage is applied. This can be confirmed by rotating the alignment axis by 45 °, but without light coming through the analyzer. In contrast, in FIG. 12B, a voltage lower than that of FIG. 12A was applied to 6.5 Vm ^-1 at 1 Hz. At this time, it was confirmed that the polarized light leaks slightly through the analyzer because the movement of the molecule is not constant due to the lower voltage, and when the alignment axis is rotated by 45 °, the light passes through the analyzer and a large amount of light And it was confirmed that it permeates. In Fig. 13A, a voltage of 15 Vm < ^-1 > of 10 Hz was applied under the condition of 200 DEG C, which corresponds to a higher frequency, as compared with Fig. When the voltage was applied, it was confirmed that the molecules were parallel to the alignment axis and the polarized light could not pass through the analyzer. However, when the alignment axis was turned by 45 °, it was confirmed that the light passed through the analyzer. It was predicted that the molecules would be oriented in the direction of the electric field in a state where the molecules could not keep up with the rate of change of the voltage due to the high frequency as compared with FIG. FIG. 13B shows a case where a voltage of 6.5 Vm- ¹ at 10 Hz is applied. Unlike FIG. 12A, molecules are arranged in parallel with the alignment axis so that the polarized light can not pass through the analyzer. It was confirmed that it came out through an analyzer. This is considered to be due to the fact that the molecules can not keep up with the change of the voltage due to the higher frequency than the case of FIG. 12B.

14 shows the results of observation of the compound of formula (1a-3) prepared in Example 9 at 160 占 폚 in the SmX phase. FIG. 14A shows a state in which no voltage is applied, and it is confirmed that the crystal orientation is larger than that of a general nematic phase, but the orientation direction is similarly oriented along the horizontal orientation surface. When an AC voltage of 12.8 Vm < ^-1 > at 10 Hz was applied thereto, it was confirmed that the polarized light could not pass through the analyzer as shown in Fig. 14B. This is thought to be due to the molecules being arranged perpendicular to the orientation axis along the electric field direction. Referring to FIG. 14C, when the applied voltage was removed, the molecules could not be found immediately, but after a lapse of time, the structure was found as shown in FIG. 14A, which takes time to re-form the layer structure .

Although the present invention has been described in terms of the preferred embodiments mentioned above, it is possible to make various modifications and variations without departing from the spirit and scope of the invention. It is also to be understood that the appended claims are intended to cover such modifications and changes as fall within the scope of the invention.

Claims (12)

A bending-nucleus mesogenic compound represented by the following formula (1)
[Chemical Formula 1]

In Formula 1,
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F,
Z is -C (= O) O-, or -C (= O) -,
m is an integer of 0,
n is an integer from 3 to 5,
y is an integer from 3 to 12; The method according to claim 1,
Wherein at least _three of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ of the compound represented by the formula (1) are F. The method according to claim 1,
Wherein the bending-nucleus mesogenic compound is a compound represented by the following formula (1a) or (1b):
[Formula 1a]

[Chemical Formula 1b]

In the above formula (1a) or (1b)
n is an integer of 5, 6 or 12; Producing an alkyl flexible lattice;
Preparing a benzimene compound having five benzenes and having a fluorine-substituted benzene at one end thereof in a bent form; And
Reacting the alkyl flexible lattice with a mono-isogen compound;
A method for producing a bending-nucleus mesogenic compound represented by the following formula (1)
[Chemical Formula 1]

In Formula 1,
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F,
Z is -C (= O) O-, or -C (= O) -,
m is an integer of 0,
n is an integer from 3 to 5,
y is an integer from 3 to 12; 5. The method of claim 4,
Wherein the alkyl flexible lattice is a compound represented by the following formula (2): < EMI ID =
(2)

n is an integer of 5, 6 or 12; 5. The method of claim 4,
The monometallic compound may be selected from the group consisting of 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy] benzoate or 3- (2,4,6- Carboxy) phenyl 4 [4- (hydroxy) benzoyloxy] benzoate. ≪ / RTI > The method according to claim 6,
The 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (hydroxy) benzoyloxy]
(SA1) 3-hydroxybenzaldehyde and 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate - (benzyloxy) benzoate);
(SA2) The above-mentioned 3-formylphenyl 4- (benzyloxy) benzoate, resorcinol, sodium chlorite and sodium phosphate monobasic monohydrate are reacted to prepare 3-carboxyphenyl To produce 4- (benzyloxy) benzoate (3-carboxyphenyl 4 (benzyloxy) benzoate);
(SA3) The above 3-carboxyphenyl 4- (benzyloxy) benzoate and 3,4,5-trifluorophenol were reacted to prepare 3,4,5-trifluorophenyl 3 - [4- (benzyloxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3- [4- (benzyloxy] benzoate);
(SA4) Reaction of 3,4,5-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate, Pd-C and hydrogen to give 3,4,5-trifluorophenyl 3- [ (4-hydroxy) benzoyloxy] benzoate (3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate;
(SA5) By reacting the above 3,4,5-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate and 4- (benzyloxy) benzoic acid, 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate 3- (3,4,5-trifuorophenyl carboxy) phenyl 4- [4- benzoyloxy] benzoate; and
(SA6) A process for producing 3- (3,4,5-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate, Pd- 5-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate;
≪ / RTI > by weight based on the weight of the mesogenic compound. The method according to claim 6,
The above-mentioned 3- (2,4,6-trifluorophenylcarboxy) phenyl 4 [4- (hydroxy) benzoyloxy]
(SB1) 3-hydroxybenzaldehyde and 4- (benzyloxy) benzoic acid to obtain 3-formylphenyl 4- (benzyloxy) benzoate - (benzyloxy) benzoate);
(SB2) The above-mentioned 3-formylphenyl 4- (benzyloxy) benzoate, resorcinol, sodium chlorite and sodium phosphate monobasic monohydrate were reacted to prepare 3-carboxyphenyl To produce 4- (benzyloxy) benzoate (3-carboxyphenyl 4 (benzyloxy) benzoate);
(SB3) The above 3-carboxyphenyl 4- (benzyloxy) benzoate and 2,4,6-trifluorophenol were reacted to prepare 2,4,6-trifluorophenyl 3 - [4- (benzyloxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3- [4- (benzyloxy] benzoate);
(SB4) By reacting 2,4,6-trifluorophenyl 3- [4- (benzyloxy) benzoyloxy] benzoate, Pd-C and hydrogen, 2,4,6-trifluorophenyl 3- [ (4-hydroxy) benzoyloxy] benzoate (2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate;
(SB5) By reacting the above 2,4,6-trifluorophenyl 3 - [(4-hydroxy) benzoyloxy] benzoate and 4- (benzyloxy) benzoic acid, 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate 3- (2,4,6-Trifluorophenylcarboxy) phenyl 4- [4- benzoyloxy] benzoate; and
(SB6) reacting the 3- (2,4,6-trifluorophenylcarboxy) phenyl 4- [4- (benzyloxy) benzoyloxy] benzoate, Pd- 6-trifluorophenylcarboxy) phenyl 4- [4-hydroxy) benzoyloxy] benzoate;
≪ / RTI > by weight based on the weight of the mesogenic compound. 1. A liquid crystal composition comprising a bending-nucleus mesogen compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently H or F, and at least one of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is F,
Z is -C (= O) O-, or -C (= O) -,
m is an integer of 0,
n is an integer from 3 to 5,
y is an integer from 3 to 12; 10. The method of claim 9,
Wherein the bending-nucleus mesogen compound is a compound represented by the following formula (1a) or (1b):
[Formula 1a]

[Chemical Formula 1b]

In the above formula (1a) or (1b)
n is an integer of 5, 6 or 12; 10. The method of claim 9,
Wherein the bending-nucleus mesogen compound represented by Formula 1 is contained in the liquid crystal composition in an amount of 1 to 10% by weight. A liquid crystal display device comprising the liquid crystal composition according to claim 9 in a liquid crystal layer.

Images