JP3503985B2 - New triphenylene derivatives - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound useful as a liquid crystal material, a triphenylene derivative. In recent years, liquid crystal display devices have been widely used in word processors, personal computers, televisions, and the like, and industrial activities such as related materials and devices have been actively carried out. Active development research has also been conducted on liquid crystal compounds, which are fundamental materials of liquid crystal display materials, and many compounds have been developed. These compounds are considered to be used not only for display devices but also for various applications. In addition to rod-shaped liquid crystal compounds that have been well known and used, discotic liquid crystal compounds, so-called discotic liquid crystal compounds, have recently attracted attention. A typical discotic liquid crystal compound is described in a research report by C. Destrade et al. [Mol. Cryst. Liq.
Cryst. 71, 111 (1981)], for example, benzene derivatives, triphenylene derivatives, truxene derivatives, phthalocyanine derivatives and the like. It has a structure in which a linear alkyl group, alkoxy group, substituted benzoyloxy group, or the like is radially substituted as a side chain.
Above all, a triphenylene derivative is an attractive compound that easily forms a discotic nematic phase, which is a monodomain liquid crystal phase preferable for use as an optical element. By the way, as is known for a rod-like compound which is a typical structure of a liquid crystal, a delicate difference in the structure often changes a liquid crystal phase to be formed and a transition temperature between the phases. This is not limited to the rod-shaped liquid crystal compound, but the same applies to the discotic liquid crystal compound. The required liquid crystal phase and the transition temperature between the phases differ depending on the target device. Therefore, the selection range can be expanded only by preparing various kinds of compounds, and it is possible to meet various purposes. However, many discotic liquid crystal compounds have not yet been known,
This is the same for the triphenylene derivative, which is a particularly attractive compound. Accordingly, an object of the present invention is to provide a novel triphenylene derivative useful as a liquid crystal material. As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the compound represented by the formula (1). General formula (I) R ¹ and R ² may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ar represents an aryl group. Y represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 5. Hereinafter, the general formula (I) will be described in detail. R ¹ and R ² may be the same or different and each represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl), an alkoxy group (eg, Methoxy, ethoxy, 2-methoxyethoxy). Ar
The aryl group has preferably 6 to 46 carbon atoms, and examples thereof include phenyl and naphthyl. Y represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 5. Among the compounds represented by the general formula (I), those represented by the following general formula (II) are preferable. General formula (II) R ¹ and R ² have the same meanings as in formula (I). R ³ is a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, t-butyl, t-amyl, t-octyl), an alkoxy group (eg, methoxy, Ethoxy, 2-methoxyethoxy) and a cyano group. Y represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 5; n represents 0 or an integer of 1 to 5; n is 2-5
At this time, a plurality of R ³ may be the same or different from each other. R ¹ and R ² are preferably a hydrogen atom,
Examples thereof include an alkyl group and an alkoxy group, and more preferably a hydrogen atom and an alkyl group having 1 to 15 carbon atoms. R
^{As 3} , an alkyl group, a halogen atom, an alkoxy group, and a cyano group are preferable, and more preferably, a group having 1 to 1 carbon atoms.
15 alkyl groups (for example, a t-amyl group) and a halogen atom. Preferred Y includes an oxygen atom.
m is preferably an integer of 1 to 4, more preferably an integer of 2 to 4. n is preferably 1 to 5, more preferably an integer of 2 to 3. Hereinafter, specific examples of the compound of the present invention represented by the general formula (I) are shown, but the present invention is not limited thereto. Specific examples include the substituent R of the general formula (I)
Is specifically shown. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image The synthesis of the compounds of the present invention generally involves
This is possible by esterification of 3,6,7,10,11-hexahydroxytriphenylene with an acid chloride. For the esterification reaction, see Sandler, K.
aro), Organic Functional Group
Preparations Part 1 (Organic Functional G
roup Preparations Part1) See Chapter 10, Academic press, 1968. The base used in the reaction includes pyridine, triethylamine, diisopropylethylamine and the like.
It can be selected from secondary amines. Preferred bases include pyridine. The solvent used in the reaction can be selected from polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, pyridine and the like, and halogen solvents such as chloroform and dichloromethane.
Preferred solvents include N, N-dimethylformamide, acetonitrile, pyridine, and more preferably pyridine. The reaction temperature is from -80 ° C to 1
It can be selected from the range of 50 ° C. -10 ° C to 100
C. is preferred, more preferably in the range of 10C to 50C. 2,3,6,7,10,11
-The synthesis method of hexamethoxytriphenylene is advanced
It is described on page 40 of Material. 2 (1990) No. 2, and in the present invention, was synthesized according to the formulation.
In addition, 2,3,6,7,10,11-hexahydroxytriphenylene was similarly used during the synthesis of 2,3,6,7,10,11-hexaacetoxytriphenylene described in the above document. Post-treatment was carried out without adding acetic anhydride to be added, and the target product was obtained in the same yield. The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The liquid crystal compound of the present invention was generally synthesized by the following route. That is, the synthesis of hexahydroxytriphenylene, the synthesis of acid chlorides and their condensation, and the synthesis route of TP-1 of the present invention is exemplified below. Embedded image Hereinafter, the method for synthesizing the liquid crystal compound of the present invention will be specifically described using TP-1 as an example. Synthesis of 2,3,6,7,10,11-hexamethoxytriphenylene (TP-A) 150 g of ferric chloride and 135 ml of ice water were put into an ice-cooled 2 liter three-necked flask and completely dissolved. 30
kg of veratrol was added. While vigorously stirring with a mechanical stirrer, 490 ml of concentrated sulfuric acid was gradually added. After 12 hours, the reaction mixture was poured into 3 liters of ice water, and after 3 hours, the precipitate was filtered and crude TP-A crystals 1
3 g (43%) were obtained. Synthesis of 2,3,6,7,10,11-hexahydroxytriphenylene (TP-B) 10.3 g of TP-A was suspended in 50 ml of dichloromethane, and 15.5 ml of boron tribromide was gradually added. Was added. Two hours later, the mixture was poured into 500 ml of ice water, extracted with 2.5 l of ethyl acetate, dried over anhydrous sodium sulfate, and filtered through celite. After the solvent was concentrated under reduced pressure, the concentrate was recrystallized from a mixed solvent of acetonitrile and dichloromethane to obtain 7.5 g (92%) of TP-B. Synthesis of α- (2,4-di-t-amylphenoxy) -acetic acid (TP-1C) In a 500 ml three-necked flask, 25 g of 2,4-di-t-amylphenol, 15 g of α-bromoacetic acid, 20 g of potassium carbonate and 100 ml of N, N-dimethylacetamide were added and stirred at 120 ° C. for 5 hours. After cooling, the reaction mixture was poured into 200 ml of water, acidified with hydrochloric acid, extracted with 300 ml of ethyl acetate and washed twice with 100 ml of water. After drying over anhydrous magnesium sulfate, the mixture was filtered and the solvent was distilled off under reduced pressure to obtain 24 g (82%) of TP-1C. 2,3,6,7,10,11-hexa (α
Synthesis of-(2,4-di-t-amylphenoxy) -acetyloxy) triphenylene (TP-1) In a 100 ml three-necked flask, 6.4 g of TP-1C and 5
Then, the mixture was heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure. to this,
0.7 g TP-B and 20 ml pyridine are added and
Stirred at C for 4 hours. After removing excess pyridine under reduced pressure, the residue was purified by silica gel column chromatography to obtain 3.15 g (80%) of TP-1. Identification data IR (cm ^-1 ) of TP-1: 2960, 2925, 2875, 1795, 1770, 1620,
1600, 1500, 1480, 1460, 1420, 1400, 1380, 1360, 12
95, 1250, 1220, 1200, 1150, 1120, 1100, 1090, 101
0, 920, 890, 810, 780 TP-3, TP-8, TP-11, TP-
31 was also synthesized by the same formulation as TP-1. Hereinafter, the respective synthesis methods will be specifically described. Synthesis of TP-3 Synthesis of α- (2,4-di-t-amylphenoxy) -butanoic acid (TP-3C)
25 g of 4-di-t-amylphenol, 18 g of 4-bromobutanoic acid, 20 g of potassium carbonate and 100 ml of N, N-dimethylacetamide were added and stirred at 120 ° C. for 5 hours. After cooling, the reaction mixture was poured into 200 ml of water, acidified with hydrochloric acid, and extracted with 300 ml of ethyl acetate.
Washed twice with ml. After drying over anhydrous magnesium sulfate, the mixture was filtered and the solvent was distilled off under reduced pressure.
%)Obtained. 2,3,6,7,10,11-hexa (γ
Synthesis of-(2,4-di-t-amylphenoxy) -butanoyloxy) triphenylene (TP-3) In a 100 ml three-necked flask, 6.4 g of TP-3C and 5
Then, the mixture was heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure. to this,
0.7 g TP-B and 20 ml pyridine are added and
Stirred at C for 4 hours. After removing excess pyridine under reduced pressure, the residue was purified using silica gel column chromatography to obtain 3.2 g (75%) of TP-3. TP-3 identification data IR (cm ^-1 ): 2960, 2950, 2900, 2875, 1765, 1620,
1600, 1500, 1475, 1460, 1450, 1420, 1400, 1380, 13
60, 1295, 1245, 1220, 1200, 1150, 1120, 1100, 105
0, 1000, 960, 920, 895, 810, 780, 750, 670
Synthesis of TP-8 Synthesis of γ- (4-t-amyl-2-chlorophenoxy) -butanoic acid (TP-8C) In a 500 ml three-necked flask, 4-t-amyl-2-chlorophenol was added. 20 g, 4-bromobutanoic acid 18 g, potassium carbonate 20 g and N, N-dimethylacetamide 10
0 ml was added and the mixture was stirred at 120 ° C. for 5 hours. After cooling, the reaction mixture was poured into 200 ml of water and acidified with hydrochloric acid.
Extracted with 0 ml of ethyl acetate and washed twice with 100 ml of water. After drying over anhydrous magnesium sulfate, the mixture was filtered and the solvent was distilled off under reduced pressure to obtain 24.2 g (78%) of TP-8C. 2,3,6,7,10,11-hexa (γ
Synthesis of-(4-t-amyl-2-chlorophenoxy) -butanoyloxy) triphenylene (TP-8) In a 100 ml three-necked flask, 6.4 g of TP-8C and 5
Then, the mixture was heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure. to this,
0.7 g TP-B and 20 ml pyridine are added and
Stirred at C for 4 hours. After removing excess pyridine under reduced pressure, the residue was purified using silica gel column chromatography to obtain 2.67 g (78%) of TP-8. TP-8 identification data IR (cm ^-1 ): 2960, 2955, 2880, 1765, 1680, 1620,
1600, 1510, 1495, 1475, 1440, 1420, 1380, 1360, 12
90, 1260, 1220, 1200, 1140, 1120, 1090, 1060, 104
0, 880, 810, 780, 720 Synthesis of TP-11 Synthesis of α- (2,4-di-t-amylphenoxy) -propionic acid (TP-11C) -Di-t-amylphenol 25 g, 2-bromopropionic acid 15.3 g,
20 g of potassium carbonate and 100 ml of N, N-dimethylacetamide were added and stirred at 120 ° C. for 5 hours. After cooling,
The reaction mixture was poured into 200 ml of water and acidified with hydrochloric acid.
Extracted with 300 ml of ethyl acetate and washed twice with 100 ml of water. After drying over anhydrous magnesium sulfate, the mixture was filtered and the solvent was distilled off under reduced pressure to obtain 26 g (85%) of TP-11C. 2,3,6,7,10,11-hexa (α
Synthesis of-(2,4-di-t-amylphenoxy) -propanoyloxy) triphenylene (TP-11) In a 100 ml three-necked flask, 6.4 g of TP-11C and 5 ml of thionyl chloride were added and heated for 2 hours. Refluxed. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure. To this, 0.7 g of TP-B and 20 ml of pyridine were added,
The mixture was stirred at 40 ° C for 4 hours. After removing excess pyridine under reduced pressure, the residue was purified using silica gel column chromatography to obtain 3.12 g (76%) of TP-11. Identification data IR (cm ^-1 ) of TP-11: 2960, 2930, 2850, 1790, 1770, 1620,
1600, 1500, 1475, 1460, 1410, 1400, 1380, 1360, 12
95, 1250, 1220, 1200, 1150, 1130, 1100, 1090, 101
0,920,890,810,770 Synthesis of TP-31 α- (4-t-amylphenoxy) -acetic acid (TP-31
In a 500 ml three-necked flask, 17 g of 4-t-amylphenol, 15 g of α-bromoacetic acid, 20 g of potassium carbonate and 100 ml of N, N-dimethylacetamide were placed.
Stirred at 0 ° C. for 5 hours. After cooling, the reaction mixture is
After pouring the mixture into acid and acidifying with hydrochloric acid, the mixture was extracted with 300 ml of ethyl acetate and washed twice with 100 ml of water. After drying over anhydrous magnesium sulfate, filtration was performed, and the solvent was distilled off under reduced pressure.
19.6 g (88%) of 31C was obtained. 2,3,6,7,10,11-hexa (α
Synthesis of-(4-t-amylphenoxy) -acetyloxy) triphenylene (TP-31) In a 100 ml three-necked flask, 6.4 g of TP-31C and 5 ml of thionyl chloride were placed, and heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure. To this, 0.7 g of TP-B and 20 ml of pyridine were added,
The mixture was stirred at 40 ° C for 4 hours. After removing excess pyridine under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2.49 g (80%) of TP-31. Identification data IR (cm ^-1 ) of TP-31: 2960, 2955, 2880, 1765, 1690, 1625,
1605, 1520, 1495, 1480, 1435, 1420, 1375, 1360, 12
90, 1260, 1220, 1195, 1140, 1110, 1080, 1050, 103
0, 880, 810, 780, 740 For reference, the phase transition temperatures of crystals of TP-3 and TP-8 by DSC and observation with a polarizing microscope are shown. TP-3 phase transition temperature crystalline phase-115 ° C.-liquid crystal phase-150 ° C.-isotropic liquid Phase transition temperature crystal phase of TP-8-110 ° C.-liquid crystal phase-122 ° C.-isotropic liquid As described above, it has been found that the novel triphenylene derivative provided by the present invention has a characteristic of exhibiting liquid crystallinity. Therefore, the compound of the present invention is useful as a novel liquid crystal material.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-258170 (JP, A) JP-A-7-258167 (JP, A) Table 9-9505312 (JP, A) Table 9- 502164 (JP, A) Special Table Hei 8-511512 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 69/712 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] A compound represented by the following general formula (I). General formula (I) R ¹ and R ² may be the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Ar represents an aryl group. Y is an oxygen atom,
Represents a sulfur atom. m represents an integer of 1 to 5.