KR101039443B1 - Method for preparing triphenylene-based reactive mesogen comprising regioselective sulfide in the side branch - Google Patents

Abstract

The present invention relates to a method for synthesizing a triphenylene-based discotic liquid crystal compound having a photoreactive group capable of forming a film by photocrosslinking and containing sulfide on a side branch for controlling a liquid crystal phase temperature range. More particularly, the present invention relates to a method for synthesizing a discotic liquid crystal compound having various lengths of alkyl side chains containing sulfur in the center of triphenylene and photoreactive groups such as acrylate, acrylamide, cinnamate, cinnamid for photocrosslinking.

Liquid Crystal Display, Compensation Film, Triphenylene, Liquid Crystal, Reactive Mesogen, Discoid Liquid Crystal

Description

Synthetic method of reactive mesogens based on triphenylene core with sulfide side chain}

The present invention relates to a method for synthesizing a triphenylene-based discotic liquid crystal compound having a photoreactive group capable of forming a film by photocrosslinking and containing sulfide on a side branch for controlling a liquid crystal phase temperature range.

Among the currently known LCD operation modes, TN (twisted nematic) and STN (super twisted nematic) 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 depending on the viewing angle in the TN-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 by using a liquid crystal film of opposite direction while having a change value of the phase difference with increasing viewing angle. For such a compensation film, discotic liquid crystal compounds capable of crosslinking and having a large negative birefringence are urgently required.

A disk-shaped liquid crystal compound usable for optical purposes, such as for the compensation film, was synthesized, and the present invention relates to a synthesis method thereof. In this research group, a triphenylene-based disk-shaped liquid crystal compound having a photoreactive group capable of forming a film by photocrosslinking and having an acyl group containing a sulfide on its side for controlling the temperature range of the liquid crystal has a large negative birefringence. When used as it was confirmed to exhibit excellent properties.

Therefore, the present invention provides a method for producing the triphenylene-based disk-shaped liquid crystal compound for supplying a large amount of the triphenylene-based disk-shaped liquid crystal compound and in high yield.

Therefore, the present invention has a photoreactive group capable of forming a film by the optical cross-linking having an excellent optical viewing angle as described above for producing a triphenylene-based discotic liquid crystal compound containing sulfide at the side for controlling the temperature range of the liquid crystal phase in high yield. It is to provide a manufacturing method.

The inventors of the present invention, ① triphenylene center and ② side branches containing sulfide for various liquid crystal phase temperature control ③ disk-like liquid crystal reactive mesogen compounds having a reactive group capable of optical crosslinking to form a film by optical crosslinking for wide viewing angle We studied the manufacturing method to secure the possibility of being useful as a compensation film and to mass produce it.

The compound corresponding to the production method of the present invention has an acrylate, acrylamide, cinnamate, cinnamid group having a sulfide group in the middle of the side branch of the liquid crystal compound centered on triphenylene and crosslinking by photoreaction at the terminal. It is to provide a production method for the triphenylene-based disk-shaped liquid crystal molecules of the general formula (1) introduced.

[Formula 1]

[In Formula 1,

R = H, Alkyl, any one selected from Aryl,

X is one selected from O or NH,

Y =

Is one selected from.]

In addition, the substituents R, X, and Y may be independently selected from the substituents defined above as necessary.

Synthesis method of the triphenylene-based disk-shaped liquid crystal molecules described above for the present invention can be prepared by the same process as the reaction scheme of Chemical Scheme 1 to Chemical Scheme 13.

In addition, another manufacturing method of the present invention may be prepared by the method described in Chemical Scheme 14 to Chemical Scheme 33.

A brief description of these manufacturing methods is given below.

Y is a form of the general formula (I) of the present invention in the form of a general formula (I) of the present invention _{- (CH 2) m -S- (} CH 2) n - has to if to by the reaction of formula (2) and (3) To prepare a compound of formula (1). The present invention is characterized in that to produce a disk-type liquid crystal high purity pure by performing each manufacturing step sequentially, the production conditions such as the temperature or molar ratio of each step is usually selected by those skilled in the art and conditions of the embodiment It will be described in the embodiment because it can be changed in the range of the.

[Formula 2]

(3)

[Formula 1]

[In Formulas 1 to 3, independently of each other

A is -OH or -NH ₂ ,

R is H,

X is one selected from O or NH, and X "is Cl or Br,

이다.]Y is

to be.]

인 경우는 하기 반응식 1 및 반응식 2를 순차적 단계로 제조하고, A가

인 경우는 하기 반응식 1, 반응식 2 및 반응식 3을 순차적 단계로 제조한다. In the reaction, in Formula 2,

In the case of the following reaction scheme 1 and scheme 2 are prepared in sequential steps, A is

In the case of the following scheme 1, scheme 2 and scheme 3 are prepared in sequential steps.

Scheme 1

Scheme 2

Scheme 3

인 경우에는 하기 화학식 4 및 화학식 5의 반응에 의해 제조되는 화학식 1의 트리페닐렌유도체의 제조한다.In another embodiment of the present invention, Y is

In the case of the triphenylene derivative of formula (1) prepared by the reaction of formulas (4) and (5).

[Formula 4]

[Chemical Formula 5]

[Formula 1]

[In Formula 1, Formula 4 and 5, independently of each other

R is H,

이고,

ego,

X is one selected from O or NH, and X "is Cl or Br,

이다.]Y is

to be.]

Formula 5 has a step of preparing by reacting the following Scheme 4 and Scheme 5.

Scheme 4

Scheme 5

When the above step is described in more detail, it can be represented by the following chemical scheme. Specific reaction temperatures, reaction ratios, treatment methods, and the like are described in the Examples, and those skilled in the art can variously react by referring to the description of the Examples. In the present invention, this description is mainly described by chemical reactions, since those skilled in the art can better explain the reaction steps to those skilled in the art when the reaction steps are described separately rather than separately.

In the preparation method of the present invention, 2,3,6,7,11-hexahydroxytriphenylene is used as a starting material, and then reacted with dihaloalkane,

[Chemical Scheme 1]

[Chemical Scheme 2]

[Chemical Scheme 3]

[Chemical Scheme 4]

[Chemical Scheme 5]

[Scheme 6]

[Scheme 7]

[Chemical Scheme 8]

[Scheme 9]

[Chemical Scheme 10]

[Chemical Scheme 11]

[Chemical Scheme 12]

[Chemical Scheme 13]

[Chemical Scheme 14]

[Chemical Scheme 15]

[Chemical Scheme 16]

[Chemical Scheme 17]

[Chemical Scheme 18]

[Chemical Scheme 19]

[Scheme 20]

[Chemical Reaction 21]

[Reaction Scheme 22]

[Chemical reaction 23]

[Chemical Scheme 24]

[Scheme 25]

[Chemical Scheme 26]

[Chemical reaction 27]

[Reaction Scheme 28]

[Scheme 29]

[Scheme 30]

[Chemical Scheme 31]

[Chemical Scheme 32]

[Reaction Scheme 33]

The triphenylene-based disk-shaped liquid crystal compound having a photoreactive group capable of forming a film by photo-crosslinking according to the present invention and having an acyl group containing a sulfide on its side for controlling the temperature range of the liquid crystal has a large negative birefringence. When it is used as, it has the effect of showing excellent characteristics and mass production is possible with this manufacturing method.

Hereinafter, the compound according to the present invention will be described by specific examples, and the embodiment of the present invention describes a method for preparing the triphenylene-based liquid crystal compound according to the present invention, and the present invention is limited only to the examples. Various embodiments can be carried out at the level of those skilled in the art, and the present invention includes all if it is within the scope of Formula 1.

Example 1 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-acryloyloxypentylthio) hexyloxy)-triphenylene

Synthesis of 2,3,6,7,10,11-hexakis (6-bromohexyloxy) triphenylene

In a 250 mL round bottom flask, 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) (1.0 g, 3.08 mmol) and potassium carbonate (8.5 g, 61.68 mmol) were added and acetone (500 mL) was added. 1,6-dibromohexane (9.0 g, 37.01 mmol) was added thereto. After the reaction mixture was refluxed for 48 hours, the solvent was evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / Hexane = 6/4) to obtain a white solid compound (3.6 g, 90%). mp (DSC) 55 ^o C; ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.60 (m, 24H), 1.97 (m, 24H), 3.48 (t, J = 6.5 Hz, 12H), 4.26 (t, J = 6.5 Hz, 12H), 7.86 (s, 6H); MS (FAB) Calcd. for C ₅₄ H ₇₈ Br ₆ O ₆ 1302, Found 1302 (M +). From the identification data, it was confirmed that 2,3,6,7,10,11-hexakis (6-bromohexyloxy) triphenylene was synthesized.

Synthesis of 2,3,6,7,10,11-hexakis (6- (5-hydroxypentylthio) hexyloxy) triphenylene

In a 250 mL round bottom flask, 2,3,6,7,10,11-hexakis (6-bromohexyloxy) triphenylene (1.0 g, 0.77 mmol) and 1-mercapto-pentanol (664 mg, 5.53 mmol) prepared above, Cesium carbonate (2.0 g, 6.14 mmol) and tetrabutylammonium iodide (2.3 g, 6.14 mmol) were added thereto and dissolved in DMF (250 mL), followed by stirring at 50 ° C for 12 hours. Water was added to terminate the reaction and extracted with dichloromethane. The solvent was evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / MeOH = 9/1) to give a light brown compound (720 mg, 61%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.44-2.54 (m, 84H), 2.54 (m, 24H), 3.66 (m, 12H), 4.26 (m, 12H), 7.86 (s, 6H).

Synthesis of 2,3,6,7,10,11-hexakis (6- (5-acryloyloxypentylthio) hexyloxy) -triphenylene

In a 250 mL round bottom flask, 2,3,6,7,10,11-hexakis (6- (5-hydroxypentyl-thio) hexyloxy) triphenylene (1.0 g, 0.65 mmol) and N, N'-dimethylaniline (709 mg, 5.85 mmol) and 4-methoxyhydroquinone (8 mg, 0.07 mmol) were added to dioxane (250 mL) to dissolve, followed by acrylroyl chloride (529 mg, 5.85 mmol). After stirring at 60 ° C. for 12 hours, the solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 2/8) (720 mg, 59%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.44-2.54 (m, 84H), 2.54 (m, 24H), 3.66 (m, 12H), 4.26 (m, 12H), 7.86 (s, 6H).

[Example 2] Synthesis of 2,3,6,7,10,11-hexakis (6- (5-acryloylaminopentylthio) hexyloxy) triphenylene

Synthesis of 2,3,6,7,10,11-hexakis (6-mercaptohexyloxy) triphenylene

In a 250 mL round bottom flask, 2,3,6,7,10,11-hexakis (6-bromohexyloxy) triphenylene (1.0 g, 0.77 mmol) and thiourea (351 mg, 4.61 mmol) synthesized above were added and ethanol (100 mL), and after stirring at room temperature for 24 hours, the solvent was evaporated. After recrystallization in ethanol, the filtered solid was dissolved in THF again, sodium hydroxide (4 g) was added and stirred at room temperature for 4 hours. After evaporation of all the solvents were separated by column chromatography (silica, CH ₂ Cl ₂ ) to give a light brown compound (588 mg, 75%).

Synthesis of 2,3,6,7,10,11-hexakis [6- (5-bromopentylthio) hexyloxy] triphenylene

In a 500 mL round bottom flask, 2,3,6,7,10,11-hexakis (6-mercaptohexyloxy) triphenylene (1.0 g, 0.98 mmol) synthesized above was added thereto, followed by DMF (250 mL). Dibromopentane (4.5 mL, 19.58 mmol) was added thereto, and cesium carbonate (2.1 g, 6.46 mmol) was added thereto. The reaction mixture was stirred at room temperature for 12 hours and then water was added to stop the reaction and extracted with ether. After evaporation of all solvents, the residue was separated by column chromatography (silica, CH ₂ Cl ₂ ) to obtain a yellow compound (1.3 g, 70%).

Synthesis of 2,3,6,7,10,11-hexakis [6- (5-aminopentylthio) hexyloxy] triphenylene

Into a 250 mL round bottom flask, 2,3,6,7,10,11-hexakis [6- (5-bromopentylthio) hexyloxy] triphenylene (500 mg, 0.26 mmol) synthesized above was added and DMF (50 mL) was added. After melting, sodium azide (428 mg, 6.58 mmol) was added thereto, and the mixture was stirred at 50 ° C. for 2 hours. Water was added to the reaction vessel, extracted with ether, and all solvents were evaporated. After ethanol and THF were added to the semi-applicator and dissolved again, Pd / C (350 mg) was added and shaken in a hydrogen reactor for 12 hours. The remaining Pd / C was filtered off and the solvents were all evaporated to give a light brown compound (380 mg, 95%).

Synthesis of 2,3,6,7,10,11-hexakis (6- (5-acryloylaminopentylthio) hexyloxy) -triphenylene

Into a 100 mL round bottom flask, add 2,3,6,7,10,11-hexakis [6- (5-aminopentylthio) hexyloxy] triphenylene (500 mg, 0.33 mmol) synthesized above, add THF to dissolve it, and then add triethylamine ( 2 mL) was added and acryloyl chloride (591 mg, 6.53 mmol) was slowly added dropwise. The reaction mixture was stirred for 12 hours at room temperature, water was added thereto, and extracted with ethyl acetate. The solvents were all evaporated and separated by column chromatography (silica, CH 2 Cl 2 / EtOAc = 1/1) to give a pale yellow compound (497 mg, 82%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.45-2.54 (m, 84H), 2.54 (m, 12H), 3.00 (m, 12H), 3.67 (m, 12H), 4.25 (m, 12H), 7.86 ( s, 6H).

Example 3 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-cinnamoyloxypentylthio) hexyloxy)-triphenylene

2,3,6,7,10,11-hexakis (6- (5-hydroxypentyl-thio) hexyloxy) triphenylene (500 mg, 0.33 mmol) was added to a 10 0 mL round bottom flask and THF (20 mL) was dissolved. Then cinnamoyl chloride (541 mg, 3.25 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 8/2) (603 mg, 80%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.24-1.75 (m, 84H), 1.92-1.99 (m, 12H), 2.45 (m, 24H), 4.21-4.27 (m, 24H), 6.46 (d, J = 16.4 Hz, 6H), 7.37 -7.54 (m, 30H), 7.70 (d, J = 16.2 Hz, 6H), 7.86 (s, 6H).

Example 4 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-cinnamoylaminopentylthio) hexyloxy) triphenylene

2,3,6,7,10,11-hexakis (6- (5-aminopentyl-thio) hexyloxy) triphenylene (500 mg, 0.27 mmol) was added to a 100 mL round bottom flask and THF (20 mL) was dissolved. Cinnamoyl chloride (449 mg, 2.69 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated, and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 8/2) (530 mg, 85%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.24-1.80 (m, 84H), 1.90-1.98 (m, 12H), 2.44 (m, 24H), 2.97 (t, 12H), 4.25 (m, 12H), 6.45 (d, J = 16.4 Hz, 6H), 7.37 -7.50 (m, 30H), 7.72 (d, J = 16.2 Hz, 6H), 7.86 (s, 6H).

Example 5 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-naphthylacryloyloxypentylthio) -hexyloxy) triphenylene

2,3,6,7,10,11-hexakis (6- (5-hydroxypentyl-thio) hexyloxy) triphenylene (350 mg, 0.23 mmol) was added to a 100 mL round bottom flask and THF (20 mL) was dissolved. Naphthyloyl chloride (493 mg, 2.28 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 9/1) (507 mg, 85%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.25-1.72 (m, 84H), 1.92-2.01 (m, 12H), 2.43 (m, 24H), 4.21-4.28 (m, 24H), 6.37 (d, J = 6.0 Hz, 6H), 7.38 (m, 6H), 7.59 -7.80 (m, 36H), 7.78 (s, 6H), 8.01 (m, 6H).

Example 6 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-naphthylacryloylaminopentylthio) -hexyloxy) triphenylene

2,3,6,7,10,11-hexakis (6- (5-aminopentyl-thio) hexyloxy) triphenylene (500 mg, 0.33 mmol) was added to a 100 mL round bottom flask and THF (25 mL) was dissolved. Naphthyloyl chloride (707 mg, 3.26 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated, and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 8/2) (750 mg, 88%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.24-1.72 (m, 84H), 1.90-2.02 (m, 12H), 2.44 (m, 24H), 2.96 (t, 12H), 4.24 (t, 12H), 6.35 (d, J = 6.0 Hz, 6H), 7.38 (m, 6H), 7.60 -7.80 (m, 36H), 7.78 (s, 6H), 8.05 (m, 6H).

Example 7 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-biphenylacryloyloxypentylthio) -hexyloxy) triphenylene

2,3,6,7,10,11-hexakis (6- (5-hydroxypentyl-thio) hexyloxy) triphenylene (500 mg, 0.33 mmol) was added to a 100 mL round bottom flask and THF (25 mL) was dissolved. 4-phenylbenzoyl chloride (789 mg, 3.25 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated, and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 9/1) (722 mg, 80%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.21-1.75 (m, 84H), 1.90-2.00 (m, 12H), 2.44 (t, 24H), 4.21-4.28 (m, 24H), 6.46 (m, 6H ), 7.38 (m, 12H), 7.40-7.75 (m, 42H), 7.82 (s, 6H).

Example 8 Synthesis of 2,3,6,7,10,11-hexakis (6- (5-biphenylacryloylaminopentylthio) -hexyloxy) triphenylene

2,3,6,7,10,11-hexakis (6- (5-aminopentyl-thio) hexyloxy) triphenylene (500 mg, 0.33 mmol) was added to a 100 mL round bottom flask and THF (25 mL) was dissolved. 4-phenyl benzoyl chloride (792 mg, 3.26 mmol) was added. Pyridine (5 mL) was added to the reaction vessel, stirred at room temperature for 24 hours, the solvents were all evaporated, and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 7/3) (678 mg, 75%). . ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.20-1.77 (m, 84H), 1.90-2.02 (m, 12H), 2.45 (m, 24H), 4.23 (t, 12H), 6.45 (m, 6H), 7.38 (m, 12 H), 7.40-7.77 (m, 42 H), 7.80 (s, 6 H).

Example 9 Synthesis of 2,3,6,7,10,11-hexakis (4- (6- (5-acryloyloxypentylthio) -hexyloxy) benzoyloxy) triphenylene

Synthesis of 6- (5-hydroxypentylthio) -1-bromohexane

1,6-dibromohexane (24.4 g, 99.83 mmol) and 5-mercapto-1-pentanol (10.0 g, 83.19 mmol) were added to a 500 mL round bottom flask, followed by melting with ethanol (250 mL) and THF (100 mL). Sodium ethoxide (6.8 g, 99.83 mmol) was added and stirred at rt for 12 h. Water was added to the reaction vessel to stop the reaction and extracted with 250 mL of ether. After removing all solvents, the residue was separated by column chromatography (silica, CH ₂ Cl ₂ ) 17.2 g, 73%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.42-1.92 (m, 14H), 2.50 (m, 4H), 3.44 (t, 2H), 3.67 (t, 2H).

Synthesis of 4- (6- (5-hydroxypentylthio) hexyloxy) benzoic acid

4-hydroxybenzoic acid (3.9 g, 28.24 mmol) and potassium carbonate (24.4 g, 176.51 mmol) were added to a 250 mL round bottom flask, and DMF (100 mL) was added thereto, followed by stirring at 50 ° C. for 1 hour. 6- (5-hydroxypentylthio) -1-bromohexane (10.0 g, 35.30 mmol) synthesized above was added to the reaction vessel and stirred at 50 ° C. for 12 hours. Water was added to the reaction vessel to stop the reaction, and after removing all solvents, the reaction mixture was separated by column chromatography (silica, CH ₂ Cl ₂ ) 8.5 g, 85%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.40-1.95 (m, 14H), 2.51 (m, 4H), 3.44 (t, 2H), 4.06 (t, 2H), 7.14 (d, 2H), 8.09 ( d, 2H), 13.51 (s, 1H).

Synthesis of 4- (6- (5-acryloyloxypentylthio) hexyloxy) benzoic acid

In a round bottom flask, 4- (6- (5-hydroxypentylthio) hexyloxy) benzoic acid (2.0 g, 5.87 mmol) synthesized above was added, dissolved in THF (150 mL), NEt ₃ (5 mL) was added, and acryloyl chloride (797 mg, 8.81 mmol) was added slowly and stirred at room temperature for 12 hours. Solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 8/2) (5.6 g, 70%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.40-1.95 (m, 14H), 2.43 (m, 4H), 4.06-4.16 (m, 4H), 5.81 (d, 1H), 6.07 (m, 1H), 6.46 (m, 1H), 7.10 (d, 2H), 8.10 (d, 2H), 13.51 (s, 1H).

Synthesis of 2,3,6,7,10,11-hexakis (4- (6- (5-acryloyloxypentylthio) -hexyloxy) benzoyloxy) triphenylene

In a 250 mL round bottom flask, 4- (6- (5-acryloyloxypentyl-thio) hexyloxy) benzoic acid (4.38 g, 11.10 mmol) synthesized above was added thereto, dissolved in SOCl ₂ (50 mL), and refluxed for 4 hours. . After removing all of SOCl ₂ , it was dissolved in CH ₂ Cl ₂ again, HHTP (500 mg, 1.54 mmol) was added, NEt ₃ (5 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. Solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 8/2) (2.3 g, 58%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.40-1.95 (m, 84H), 2.43 (m, 24H), 4.06-4.16 (m, 24H), 5.81 (d, 6H), 6.07 (m, 6H), 6.46 (m, 6H), 7.10 (d, 12H), 8.10 (d, 12H), 8.42 (s, 6H). The synthesized liquid crystal compound was irradiated with ultraviolet light (365 nm) using a photoinitiator, and then thermally crosslinked at 30 ° C. for 30 minutes at a light crosslinking. Could get a picture. From Figure 1 it can be confirmed that the nematic liquid crystal phase is maintained by the crosslinking, which is expected to express excellent properties as the optical compensation film.

Example 10 Synthesis of 2,3,6,7,10,11-hexakis (4- (6- (5-cinnamoyloxypentylthio) -hexyloxy) benzoyloxy) triphenylene

Synthesis of 4- (6- (5-cinnamoyloxypentylthio) hexyloxy) benzoic acid

In a 250 mL reaction flask, 4- (6- (5-hydroxypentylthio) hexyloxy) benzoic acid (1.0 g, 2.94 mmol) synthesized above was added, dissolved in THF (100 mL), and NEt ₃ (5 mL) was added thereto. Cinnamoyl chloride (734 mg, 4.41 mmol) was added slowly and stirred at room temperature for 12 hours. Solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 7/3) (1.1 g, 80%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.41-1.94 (m, 14H), 2.44 (t, 4H), 4.09-4.15 (m, 4H), 6.40 (d, 1H), 7.21-7.54 (m, 7H ), 7.64 (d, 1 H), 8.10 (d, 2 H), 13.12 (s, 1 H).

Synthesis of 2,3,6,7,10,11-hexakis (4- (6- (5-cinnamoyloxypentylthio) -hexyloxy) benzoyloxy) triphenylene

In a 250 mL round bottom flask, 4- (6- (5-cinnamoyloxypentyl-thio) hexyloxy) benzoic acid (5.2 g, 11.1 mmol) was added and dissolved in SOCl ₂ (50 mL), followed by reflux for 4 hours. After removing all of SOCl ₂ , it was dissolved in CH ₂ Cl ₂ again, HHTP (500 mg, 1.54 mmol) was added, NEt ₃ (5 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. Solvents were all evaporated and separated by column chromatography (silica, CH ₂ Cl ₂ / EtOAc = 7/3) (3.5 g, 75%). ¹ H NMR (200 MHz, CDCl ₃ ) δ 1.40-1.95 (m, 84H), 2.44 (t, 24H), 4.10-4.15 (m, 24H), 6.40 (d, 6H), 7.20-7.55 (m, 42H ), 7.63 (d, 6H), 8.10 (d, 12H), 8.41 (s, 6H).

1 is a liquid crystal phase polarization micrograph of synthesized 2,3,6,7,10,11-hexakis (4- (6- (5-acryloyloxypentylthio) -hexyloxy) benzoyloxy) triphenylene.

Claims (4)

A method for preparing Formula 1 prepared by the reaction of Formulas 2 and 3 below. [Formula 2]

(3)

[Formula 1]

[In Formulas 1 to 3, independently of each other A is -OH or -NH ₂ , R is H,

X is one selected from O or NH, and X "is Cl or Br, Y is

to be.] The method of claim 1, A

In the case of the following reaction scheme 1 and scheme 2 are prepared in sequential steps, A is

In the case of preparing the following reaction scheme 1, scheme 2 and scheme 3 in a sequential step. Scheme 1

Scheme 2

Scheme 3

[M = 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16 and n = 2, 3, 4, 5, 6, 7, 8, 9 in Schemes 1 to 3 above. , 10, 12, 16.] Method for producing a triphenylene derivative of formula (1) prepared by the reaction of formulas (4) and (5). [Formula 4]

[Chemical Formula 5]

[Formula 1]

[In Formula 1, Formula 4 and 5, independently of each other R is H,

X is one selected from O or NH, and X "is Cl or Br, Y is

to be.] The method of claim 3, Formula 5 is prepared by the reaction of Scheme 4 and Scheme 5 sequentially. Scheme 4

Scheme 5

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