KR101255062B1 - Halogen containing reactive mesogens based on triphenylene core - Google Patents

Abstract

The present invention relates to a liquid crystal compound for a compensation film of a liquid crystal display device, and more particularly, to a halogen-containing triphenylene-based reactive mesogen compound. The halogen-containing triphenylene-based reactive mesogen compound has a high birefringence, so that a compensation film can be manufactured in a thin film, and the liquid crystal device employing the compensation film has an advantage of realizing a wide viewing angle.

Description

Halogen containing reactive mesogens based on triphenylene core

The present invention relates to the synthesis of a halogen-containing triphenylene-based mesogen compound containing a photoreactive group capable of film formation through a photo crosslinking reaction by ultraviolet (UV) irradiation.

As digitalization and informatization are accelerated, many IT devices are used in daily life, and display technology for them is also developing. The most representative electronic display used in the past is the CRT (cathod ray tube) monitor used in TVs and computer monitors. However, because CRT monitors are bulky and heavy, they are difficult to enlarge and carry, high power consumption, and high driving voltages are gradually replacing other flat panel displays. Representative flat panel displays such as LCD, PDP, and OLED to overcome the limitations of CRT are the most common of these. LCD, which combines liquid crystal and semiconductor technology, is widely applied to large TVs, PC monitors, display devices of various measuring devices, PMP or mp3 devices, car navigation devices, mobile phones, etc. due to its thin, light and low power consumption. To realize high quality large LCD, wide viewing angle, high brightness, high contrast ratio and fast response speed are required.

Among the currently known LCD operating modes, TN (twisted nematic), STN (super twisted nematic), VA (Vertical alignment) and IPS (In-plane switching) are widely used. The rod-shaped liquid crystal molecules used in such LCDs are oriented in one direction on the polymer alignment layer, and this orientation causes a change in the apparent Δnd of the liquid crystals with respect to the viewing angle in each LCD, thereby limiting the optical viewing angle in the LCD. When the arrangement of liquid crystal molecules is changed by the application of an electric field, the traveling light meets the liquid crystal molecules at different angles, thereby causing a difference in the polarization state of the transmitted light. As a result, some of the light leaks when the transmitted light passes through the polarizer on the LCD surface. In this case, there is a difference in luminance or an inversion of contrast at the inclination angle from the front. There have been various attempts to overcome this phenomenon and to secure wide viewing angles. Currently, a method using a compensation film is relatively widely used. Compensation film is a principle of compensating using a film having an opposite direction while having a change value of a phase difference with increasing viewing angle. The wide viewing angle compensation film currently used in LCDs in TN mode is a film of a mixture containing a disk-shaped reactive liquid crystal having a negative birefringence, which is exclusively supplied by Fujifilm. The discotic liquid crystal compound used by FUJIFILM has a low birefringence value of less than 0.1, and has a disadvantage in that the thickness of the film is thick for proper light compensation. In order to overcome such current problems and to implement a highly efficient ultra thin film compensation film, a reactive liquid crystal compound having a high birefringence is urgently needed.

Various attempts have been reported for molecules of high birefringence. In general, high birefringence is possible by increasing the number of conjugated pi electrons or by introducing functional groups with large polarization. However, when the number of conjugated pi electrons is increased or when a large polarization group such as cyano or thiisocyanato is introduced, oxidative stability and light stability are greatly reduced.

The present invention provides a halogen-containing triphenylene-based reactive mesogen compound capable of producing a compensation film as a core material for a large-screen wide viewing angle liquid crystal display device;

It provides a compensation film prepared by containing the halogen-containing triphenylene-based reactive mesogen compound;

The present invention also provides an electronic device, particularly a liquid crystal display device having a compensation film manufactured using the halogen-containing triphenylene-based reactive mesogen compound.

The present invention provides a halogen-containing triphenylene-based reactive mesogenic compound of formula 1 having a photoreactive group capable of film formation by photocrosslinking and containing halogen for high birefringence.

[Formula 1]

[In Formula 1,

X is any one selected from bromine group, chloro group and iodine group,

Y Is any one selected from O, NH, S,

L is selected from -R-, -C (= 0) -R-, -C (= 0) -Ar-OR- and C (= 0) -Ar-NH-R-, wherein R is straight or branched A C ₁ -C ₂₀ alkylene group of the chain, Ar is a C ₆ -C ₃₀ arylene group,

,

,

,

,

,

,

,

로부터 선택되는 어느 하나이다.]Z is

,

,

,

,

,

,

,

Is one selected from.]

Preferably, it may be exemplified by a halogen-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).

(2)

(3)

[In Formula 2 or Formula 3, the definitions of X, Y, L, and Z are the same as in Formula 1.

More preferably, R is a straight or branched C ₁ -C ₁₂ alkylene group, Ar is any one selected from phenyl group, naphthyl group, anthracenyl group, benzopyrene group, pyrene group, phenanthrene group and fluorene group Phosphorus halogen-containing triphenylene-based reactive mesogenic compounds may be exemplified, but this does not limit the compound of the present reaction.

In addition, the halogen-containing triphenylene-based reactive mesogen compound including the formula (1) can be used as a liquid crystal compound for a compensation film, it can be used in a liquid crystal display device having such a compensation film.

The present invention provides a halogen-containing triphenylene-based reactive mesogen compound by introducing a halogen group for high birefringence and a side branch for temperature control of the liquid crystal phase, and a compensation film as a core material in a large-sized wide viewing angle liquid crystal display device. It can be produced in a thin film using a phenylene-based reactive mesogen compound.

In addition, it is expected to be effectively used in electronic devices including the liquid crystal display device having the same from a compensation film including a halogen-containing triphenylene-based reactive mesogen compound.

1 is a polarized light micrograph of the halogen-containing triphenylene-based reactive mesogen compound prepared in Example 2.

The present invention provides a halogen-containing triphenylene-based reactive mesogen compound capable of producing a compensation film, which is a core material of a liquid crystal display.

The halogen-containing triphenylene-based reactive mesogen compound of the present invention contains a halogen group for high birefringence around triphenylene and can be crosslinked by photoreaction at the terminal side of the compound with acryloyl group, methacryloyl group, and phenyl It became an acryloyl group (cinnamoyl group) or a furyl acryloyl group.

Since the halogen-containing triphenylene-based reactive mesogen compound of the present invention has a high birefringence, a compensation film of a liquid crystal display device can be manufactured in a thin film, and a liquid crystal device employing such a compensation film has an advantage of realizing a wide viewing angle. have.

In addition, since both thermosetting or photocuring are possible, there is a feature that the compensation film can be selectively manufactured according to the process conditions or the state of the substrate.

The halogen-containing triphenylene-based reactive mesogen compound of the present invention is characterized by the following formula (1).

[Formula 1]

[In Formula 1,

X is any one selected from bromine group, chloro group and iodine group,

Y Is any one selected from O, NH, S,

L is selected from -R-, -C (= 0) -R-, -C (= 0) -Ar-OR- and C (= 0) -Ar-NH-R-, wherein R is straight or branched A C ₁ -C ₂₀ alkylene group of the chain, Ar is a C ₆ -C ₃₀ arylene group,

,

,

,

,

,

,

,

로부터 선택되는 어느 하나이다.]Z is

,

,

,

,

,

,

,

Is one selected from.]

Preferably, it may be exemplified by a halogen-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).

[Formula 2]

(3)

[In Formula 2 or Formula 3, the definitions of X, Y, L, and Z are the same as in Formula 1.

More preferably, R is a straight or branched C ₁ -C ₁₂ alkylene group, Ar is any one selected from phenyl group, naphthyl group, anthracenyl group, benzopyrene group, pyrene group, phenanthrene group and fluorene group Phosphorus halogen-containing triphenylene-based reactive mesogenic compounds may be exemplified, but this does not limit the compound of the present reaction.

The halogen-containing triphenylene-based reactive mesogen compound of the general formula (1) of the present invention can be produced by the reaction described in the following reaction formulas (1) to (43).

[Scheme 1]

[Scheme 2]

[Reaction Scheme 3]

[Reaction Scheme 4]

[Scheme 5]

Scheme 6

Scheme 7

Through the schemes 1 to 7 it can be prepared a trihalogen triphenylene triol symmetrical.

Scheme 8

Scheme 9

[Reaction Scheme 10]

[Reaction Scheme 11]

[Reaction Scheme 12]

[Reaction Scheme 13]

Through the schemes 8 to 13 can be prepared an asymmetric trihalogentriphenylene triol.

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Scheme 18

Scheme 19

Scheme 20

Scheme 21

Scheme 22

Scheme 23

Scheme 24

Scheme 25

Scheme 26

Scheme 27

Scheme 28

Scheme 29

Scheme 30

Scheme 31

Scheme 32

Scheme 33

Scheme 34

Scheme 35

Scheme 36

Scheme 37

Scheme 38

Scheme 39

Scheme 40

Scheme 41

Scheme 42

Scheme 43

Through the reaction schemes 25 to 43, a photocrosslinkable halogen-containing triphenylene-based reactive mesogen compound having a symmetrical or asymmetrical halogen group introduced therein may be prepared.

The halogen-containing triphenylene-based reactive mesogen compound of the present invention has a symmetric or asymmetric triphenylene as a center and a halogen group for high birefringence, a side branch for various liquid crystal phase temperature control, and a side branch of a compound capable of photocrosslinking under various conditions. The acryloyl group, the methacryloyl group, the phenyl acryloyl group (cinnamoyl group), or the furyl acryloyl group was introduce | transduced at the terminal.

Since the halogen-containing triphenylene-based reactive mesogen compound of the present invention has a high birefringence, a compensation film of a liquid crystal display device can be manufactured in a thin film, and a liquid crystal device employing such a compensation film has an advantage of realizing a wide viewing angle. have.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto.

Example 1 Synthesis of Halogen-Containing Symmetric Disc Reactive Mesogen 2,6,10-tribromo-3,7,11-tris (4- (6-acryloyloxyhexyloxy) benzoyloxy) triphenylene

Synthesis of 2-Methoxyanisole

2-Methoxyphenol (20 g, 0.16 mol) is dissolved in acetone (500 mL), and then K ₂ CO ₃ (111 g, 0.81 mol) is added and stirred for 30 minutes. 1-bromohexane (25 mL, 0.18 mol) is added dropwise and refluxed under nitrogen atmosphere for 24 hours. After completion of the reaction, acetone is removed and extracted with dichloromethane. After removal of solvent, column chromatography (silica, hexane / CH ₂ Cl ₂ = 5/1) was separated to give 2-methoxyanisole (29 g, 88%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 6.88-6.82 (m, 4H, ArH), 3.99 (t, 2H, ArOCH ₂ ), 3.80 (s, 3H, OCH ₃ ) 1.83-1.76 (m, 2H, CH ₂ ), 1.47-1.29 (m, 6H, CH ₂ ), 0.91-0.88 (m, 3H, CH ₃ ); MS m / z 208 (M ⁺ )

Synthesis of 2,6,10-Trimethoxy-3,7,11-tris (hexyloxy) triphenylene

2-Methoxyanisole (29 g, 0.14 mol) is dissolved in dichloromethane (1 L) and then FeCl ₃ (68 g, 0.42 mol) is added dropwise. After the reaction proceeds for 24 hours, the reaction is terminated with methanol. After 3 hours, the solvent was removed, followed by column chromatography (silica, hexane / CH ₂ Cl ₂ = 2/3) to obtain a white solid (5.5 g, Yield 19%).

¹ H NMR (CDCl ₃ , 500 MHz) δ 7.76 (d, 2H, ArH), 4.23 (t, 2H, ArOCH ₂ ), 4.07 (s, 3H, OCH ₃ ), 1.98-1.92 (m, 2H, CH ₂ ) , 1.58-1.52 (m, 2H, CH ₂ ), 1.43-1.30 (m, 4H, CH ₂ ), 0.93-0.86 (m, 3H, CH ₃ ); MS m / z 618 (M ⁺ )

Synthesis of 2,6,10-Trihydroxy-3,7,11-tris (hexyloxy) triphenylene

Dissolve 2,6,10-Trimethoxy-3,7,11-tris (hexyloxy) triphenylene (0.5 g, 0.8 mmol) in THF (200 mL) and then add 0.5M lithium diphenylphosphine (6.5 mL, 3.2) under nitrogen gas. mmol) is added. After the reaction proceeds for 12 hours, the organic layer is extracted with 2M aqueous hydrochloric acid solution and dichloromethane. Separated by column chromatography (silica, hexane / CH ₂ Cl ₂ = 1/5) to give a white solid (434 mg, 94%).

¹ H NMR (CDCl ₃ , 300 MHz) δ = 7.93 (s, 3H, ArH), 7.65 (s, 3H, ArH), 5.82 (s, 3H, ArOH), 4.25 (t, 6H, ArOCH ₂ ), 1.96 ( m, 6H, CH ₂ ), 1.53 (m, 6H, CH ₂ ), 1.41-1.36 (m, 12H, CH ₂ ), 0.96 (t, 9H, CH ₃ ); MS m / z 576 (M ⁺ )

Synthesis of 2,6,10-Tris (trifluoromethanesulfonyl) -3,7,11-tris (hexyloxy) triphenylene

Dissolve 2,6,10-Trihydroxy-3,7,11-tris (hexyloxy) triphenylene (1.0 g, 1.7 mmol) in pyridine (15 mL). Trifluoromethanesulfonic anhydride (1.5 mL, 1.7 mmol) is added dropwise at 0 ^o C and stirred for 24 h. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CHCl ₃ = 2/1) to give a yellow solid (1.6 g, 92%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.30 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.92 (d, 2H, ArH), 7.85 (s, 1H, ArH), 4.38 (m, 6H, ArOCH ₂ ), 1.95 (m, 6H, CH ₂ ), 1.53 (m, 6H, CH ₂ ), 1.41-1.34 (m, 12H, CH ₂ ), 0.95 (t, 9H, CH ₃ ); MS m / z 972 (M ⁺ )

Synthesis of 2,6,10-Tris (hexyloxy) triphenylene

2,6,10-Tris (trifluoromethanesulfonyl) -3,7,11-tris (hexyloxy) triphenylene (0.5 g, 0.52 mmol), palladium (II) acetate (10 mg, 0.046 mmol), triphenylphosphine (30 mg, 0.115 mmol ) In DMF (10 mL), formic acid (0.1 mL, 3.09 mmol) and stirred at 60 ^o C for 24 h under nitrogen atmosphere. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CH ₂ Cl ₃ = 1/5) to give a yellow solid (275 mg, 99%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.40-8.33 (m, 1H, ArH), 7.90 (m, 1H, ArH), 7.25-7.20 (m, 1H, ArH), 4.15 (t, 2H, ArOCH ₂ ) , 1.90 (m, 2H, CH ₂ ), 1.50 (m, 2H, CH ₂ ), 1.41-1.36 (m, 4H, CH ₂ ), 0.93 (t, 3H, CH ₃ ); MS m / z 528 (M ⁺ )

Synthesis of 2,6,10-Tribromo-3,7,11-tris (hexyloxy) triphenylene

2,6,10-Tris (hexyloxy) triphenylene (2.5 g, 4.73 mmol) is dissolved in dichloromethane (50 mL) and bromine (65 mL, 14.92 mmol) is added dropwise at 0 ^° C. After 2 hours, the reaction was terminated with aqueous sodium thiosulfate solution and extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CH ₂ Cl ₂ = 1/1) to obtain a yellow solid (3.6 g, 99%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.50 (s, 3H, ArH), 7.62 (s, 3H, ArH), 4.25 (t, 6H, ArOCH ₂ ), 1.96 (t, 6H, CH ₂ ), 1.66- 1.60 (m, 6H, CH ₂ ), 1.43-1.39 (m, 12H, CH ₂ ), 0.95 (t, 9H, CH ₃ ); MS m / z 764 (M ⁺ )

Synthesis of 2,6,10-Trihydroxy-3,7,11-tribromotriphenylene

Dissolve 2,6,10-Tribromo-3,7,11-tris (hexyloxy) triphenylene (0.5 g 0.65 mmol) in dichloromethane (10 mL). Dilute BBr ₃ (2.2 mL, 24.1 mmol) in dichloromethane (10 mL) at -75 ^o C under nitrogen gas and add dropwise. After 24 hours, the reaction was terminated with ice water, and the resulting solid was filtered to give a white compound (268 mg, 80%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 11.0 (s, 3H, ArOH), 8.60 (s, 3H, ArH), 7.90 (s, 3H, ArH); MS m / z 512 (M ⁺ )

Synthesis of 3,7,11-tribromo-2,6,10-tris (4- (6-acryloyloxyhexyloxy) benzoyloxy) triphenylene

4- (6- (Acryloyloxy) hexyloxy) benzoic acid (0.65 g, 2.21 mmol) of methansulfonyl chloride (0.2 mL in mukhin after 0 ^o C to seven amine (0.77 mL, 5.52 mmol) in DME (30 mL) and the tree, 2.42 mmol) is added dropwise under a nitrogen atmosphere. After 3 hours, the temperature is raised to room temperature, and 4-dimethylaminopyridine (0.28 g, 0.23 mmol) and 2,6,10-trihydroxy-3,7,11-tribromotriphenylene (0.24 g, 0.46 mmol) are added thereto. After 24 hours it is extracted with dichloromethane. After solvent removal, separation by column chromatography (silica, CH ₂ Cl ₂ / MeOH = 60/1) afforded a yellow solid (319 mg, 58%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.62 (s, 3H, ArH), 8.44 (s, 3H, ArH), 8.22 (d, 6H, ArH), H), 6.90 (d, 6H, ArH), 6.45 -6.37 (m, 3H, OAcr), 6.19-6.10 (m, 3H, OAcr), 5.85-5.81 (m, 3H, OAcr), 4.20 (t, 6H, ArOCH ₂ ), 4.06 (t, 6H, ArOCH ₂ ), 1.90-1.82 (m, 8H, CH ₂ ), 1.76-1.66 (m, 6H, CH ₂ ), 1.55-1.50 (m, 10H, CH ₂ ); MS m / z 1336 (M ⁺ )

Example 2 Synthesis of Halogen-containing Asymmetric Disc Reactive Mesogen 3,6,11-tribromo-2,7,10-tris (4- (6-acryloyloxyhexyloxy) benzoyloxy) triphenylene

Synthesis of 2-Hexyloxyphenol

Catechol (50 g, 0.45 mol) is dissolved in acetone (1 L), then K ₂ CO ₃ (250 g, 1.81 mol) is added and stirred for 30 minutes. 1-bromohexane (95.6 mL, 0.68 mol) is added dropwise and refluxed for 24 hours under nitrogen atmosphere. After completion of the reaction, acetone is removed and extracted with dichloromethane. The solvent was removed and then separated by column chromatography (silica, hexane / CH ₂ Cl ₂ = 5/1) to give a colorless oil 2-hexyloxyphenol (25 g, yield 28%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 6.93-6.89 (m, 1H, ArH), 6.85-6.77 (m, 3H, ArH), 5.76 (s, 1H, ArOH) 3.99 (t, 2H, ArOCH ₂ ), 1.80-1.71 (m, 2H, CH ₂ ), 1.46-1.26 (m, 6H, CH ₂ ), 0.91 (m, 3H, CH ₃ ); MS m / z 194 (M ⁺ )

Synthesis of 2,7,10-Trihydroxy-3,6,11-tris (hexyloxy) triphenylene

2-hexyloxyphenol (2 g, 0.01 mol) is dissolved in dichloromethane (250 mL) and then FeCl ₃ (5 g, 0.03 mol) is added. After the reaction proceeds for 24 hours it is terminated with methanol. After 3 hours, the solvent was removed, followed by column chromatography (silica, hexane / CH ₂ Cl ₂ = 1/5) to obtain a white solid (0.8 g, yield 13%).

¹ H NMR (CDCl ₃ , 300 MHz) δ = 7.93 (d, 3H, ArH), 7.78 (s, 1H, ArH), 7.73 (d, 2H, ArH), 5.88-5.85 (m, 3H, ArOH), 4.31 -4.23 (m, 6H, ArOCH ₂ ), 1.97-1.91 (m, 6H, CH ₂ ), 1.57-1.54 (m, 6H, CH ₂ ), 1.40-1.38 (m, 12H, CH ₂ ), 0.94 (m , 9H, CH ₃ ) (; MS m / z 576 (M ⁺ )

Synthesis of 2,7,10-Tris (trifluoromethanesulfonyl) -3,6,11-tris (hexyloxy) triphenylene

Dissolve 2,7,10-Trihydroxy-3,6,11-tris (hexyloxy) triphenylene (0.7 g, 0.001 mol) in pyridine (10 mL). Trifluoromethanesulfonic anhydride (1.2 mL, 0.007 mol) is added dropwise at 0 ^o C and stirred for 24 h. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CHCl ₃ = 2/1) to give a yellow solid (1.1 g, 94%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.27 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.91 (d, 2H, ArH), 7.81 (s, 1H, ArH), 4.33-4.28 ( m, 6H, ArOCH ₂ ), 2.00-1.95 (m, 6H, CH ₂ ), 1.62-1.61 (m, 6H, CH ₂ ), 1.43-1.38 (m, 12H, CH ₂ ), 0.94 (m, 9H, CH ₃ ); MS m / z 972 (M ⁺ )

Synthesis of 2,7,10-Tris (hexyloxy) triphenylene

2,7,10-Tris (trifluoromethanesulfonyl) -3,6,11-tris (hexyloxy) triphenylene (0.5 g, 0.52 mmol), palladium (II) acetate (10 mg, 0.046 mmol), triphenylphosphine (30 mg, 0.115 mmol ) In DMF (10 mL), formic acid (0.1 mL, 3.09 mmol) and stirred at 60 ^o C for 24 h under nitrogen atmosphere. After completion of the reaction, the mixture was extracted with dichloromethane. After removing the solvent was separated by column chromatography (silica, hexane / CH ₂ Cl ₃ = 1/5) to give a yellow solid (270 mg, 99%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.46-8.37 (m, 1H, ArH), 7.93-7.90 (m, 1H, ArH), 7.24-7.14 (m, 1H, ArH), 4.18-4.12 (m, 2H , ArOCH ₂ ), 1.92-1.82 (m, 2H, CH ₂ ), 1.54 (m, 2H, CH ₂ ), 1.41-1.37 (m, 4H, CH ₂ ), 0.95-0.91 (m, 3H, CH ₃ ) ; MS m / z 528 (M ⁺ )

Synthesis of 2,7,10-Tribromo-3,6,11-tris (hexyloxy) triphenylene

2,7,10-Tris (hexyloxy) triphenylene (0.24 g, 0.45 mmol) is dissolved in dichloromethane (10 mL) and bromine (7.7 mL, 1.49 mmol) is added dropwise at 0 ^° C. After 2 hours, the reaction was terminated with aqueous sodium thiosulfate solution and extracted with dichloromethane. After removing the solvent was separated by column chromatography (silica, hexane / CH ₂ Cl ₂ = 1/1) to give a yellow solid (345 mg, 99%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.53 (s, 1H, ArH), 8.49 (d, 2H, ArH), 7.69 (d, 2H, ArH), 7.62 (m, 1H, ArH), 4.27-4.20 ( m, 6H, ArOCH ₂ ), 1.99-1.94 (m, 6H, CH ₂ ), 1.64-1.60 (m, 6H, CH ₂ ), 1.42-1.40 (m, 12H, CH ₂ ), 0.97-0.92 (m, 9H, CH ₃ ); MS m / z 764 (M ⁺ )

Synthesis of 2,7,10-Trihydroxy-3,6,11-tribromotriphenylene

Dissolve 2,7,10-Tribromo-3,6,11-tris (hexyloxy) triphenylene (0.62 g 0.81 mmol) in dichloromethane (10 mL). Dilute BBr ₃ (2.3 mL, 24.3 mmol) in dichloromethane (10 mL) at -75 ^o C under nitrogen gas and add dropwise. After 24 hours, the reaction was terminated with ice water, and the resulting solid was filtered to give a white compound (297 mg, 72%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 10.96 (s, 1H, ArOH), 10.77 (s, 1H, ArOH), 10.50 (s, 1H, ArOH), 8.81-8.87 (d, 2H, ArH), 8.48 ( s, 1H, ArH), 7.93-7.88 (t, 3H, ArH); MS m / z 512 (M ⁺ )

Synthesis of 3,6,11-tribromo-2,7,10-tris (4- (6-acryloyloxyhexyloxy) benzoyloxy) triphenylene

4- (6- (Acryloyloxy) hexyloxy) benzoic acid (0.65 g, 2.21 mmol) of methansulfonyl chloride (0.2 mL in mukhin after 0 ^o C to seven amine (0.77 mL, 5.52 mmol) in DME (30 mL) and the tree, 2.42 mmol) is added dropwise under a nitrogen atmosphere. After 3 hours, the temperature is raised to room temperature, and 4-dimethylaminopyridine (0.28 g, 0.23 mmol) and 2,7,10-trihydroxy-3,6,11-tribromotriphenylene (0.24 g, 0.46 mmol) are added thereto. After 24 hours it is extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, CH ₂ Cl ₂ / MeOH = 60/1) to give a yellow solid (0.38 g, 69%).

¹ H NMR (CDCl ₃ , 300 MHz) δ 8.64-8.60 (d, 2H, ArH), 8.39 (s, 1H, ArH), 8.28-8.12 (m, 8H, ArH), 8.03 (s, 1H, ArH), 6.98-6.88 (m, 6H, ArH), 6.45-6.37 (m, 3H, OAcr), 6.18-6.08 (m, 3H, OAcr), 5.85-5.82 (m, 3H, OAcr), 4.22-4.16 (m, 6H, ArOCH ₂ ), 4.08-4.02 (m, 6H, ArOCH ₂ ), 1.87-1.83 (m, 8H, CH ₂ ), 1.77-1.70 (m, 6H, CH ₂ ), 1.55-1.51 (m, 10H, CH ₂ ); MS m / z 1336 (M ⁺ )

[Experimental example] Liquid crystal evaluation of halogen-containing triphenylene-based reactive mesogen compound

 The liquid crystallinity according to the temperature of the halogen-containing triphenylene-based reactive mesogen compound synthesized in Example 2 was evaluated using a polarizing optical microscope.

As shown in the polarization optical micrograph shown in FIG. 1, it can be confirmed that the liquid is changed to an isotropic liquid at 124 ° C. during the second heating, and the liquid crystal phase appears at 106 ° C. and the liquid crystal phase is maintained at room temperature (26 ° C.). Could. This triphenylene-based reactive mesogen compound containing a side branch for controlling the liquid crystal phase temperature and containing a halogen group for high birefringence is produced as a compensation film after orientation and light irradiation in the liquid crystal phase temperature range and used as a liquid crystal display device. Reagent angles can be implemented.

Claims (5)

delete A compensation film comprising a halogen-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).
(2)

(3)

[In Formula 2 or Formula 3,
X is any one selected from bromine group, chloro group and iodine group,
Y Is any one selected from O, NH, S,
L is selected from -R-, -C (= 0) -R-, -C (= 0) -Ar-OR- and C (= 0) -Ar-NH-R-, wherein R is straight or branched A C ₁ -C ₂₀ alkylene group of the chain, Ar is a C ₆ -C ₃₀ arylene group,
Z is

,

,

,

,

,

,

,

Is one selected from.] The method of claim 2,
R is a linear or branched C ₁ -C ₁₂ alkylene group, Ar is a halogen-containing tree which is any one selected from phenyl group, naphthyl group, anthracenyl group, benzopyrene group, pyrene group, phenanthrene group and fluorene group Compensation film containing a phenylene-based reactive mesogen compound. delete A liquid crystal display device comprising the compensation film of claim 2.

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