JPH1135535A - New triphenylene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound bearing a triphenylamine derivative and a phenylcarbazole derivative as substituents, and useful as a liquid crystal material or electronic material. SOLUTION: This new compound is shown by formula I [L is a bivalent group; Q is a (substituted) diphenylaminophenyl or 9-carbazolylphenyl], e.g. a compound, wherein L-Q in formula I is shown by formula II (L is a group of formula III; X is H; Ar<1> and Ar<2> are each phenyl). The compound of formula I is obtained by introducing groups including L into a triphenylene skeleton- bearing compound such as 2,3,6,7,10,11-hexakis -(-aminopentyloxy) triphenylene by the aid of e.g. 4-carboxytriphenylamine in a solvent such as tetrahydrofuran at 100-250 deg.C. This new compound is useful as a discotic liquid crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel triphenylene derivative useful as a liquid crystal material or an electronic material.

[0002]

2. Description of the Related Art A liquid crystal, which is a liquid and exhibits a specific property of having an order in molecular arrangement, has been shown to be useful for its specificity. A typical example is a liquid crystal display (LCD), which has now reached an important industrial position. The TN or STN liquid crystal used in this LCD belongs to a rod-shaped liquid crystal if classified according to the shape of the molecule. It is supposed to be. For example, D. Adam, et al., Natur
e, vol. 371, pp. 141-143 (1994), which has a high speed as a charge transporting material and has a unique optical anisotropy described in JP-A-7-146409. This is an optical compensator utilizing the above.

Further, it is known that triphenylamine derivatives and phenylcarbazole derivatives can be used as useful materials for electrophotography and electroluminescent devices. In addition, as described in Japanese Patent Application No. 8-233467, it can play a useful role in improving the performance of a lithium ion secondary battery, which has recently become important as a power supply for portable electronic devices. Are known. It is well known that the properties and functions exhibited by a molecule in the state of a single molecule can be changed in the state of an assembled molecule, and is sometimes described by the term supramolecular. A typical example that has been known for a long time is a change in an absorption spectrum due to association of a dye. A J-aggregate showing a sharper spectrum on a longer wavelength side than an absorption wavelength in a monomolecular state is a spectral sensitization of a silver salt photograph. It is used because of its characteristics as a pigment.

[0004] Accordingly, also in the triphenylamine derivative and the phenylcarbazole derivative, useful properties and functions are expected to be similarly exhibited depending on the aggregated state. From this viewpoint, the structure of the triphenylene derivative in which a plurality of the same molecular species can be substituted and the development of liquid crystal properties are extremely interesting.

[0005] Against this background, the discovery of new compounds that can exhibit discotic liquid crystallinity and the emergence of disc-like compounds such as triphenylene derivatives having triphenylamine derivatives and phenylcarbazole derivatives as substituents are expected. I have. However, since the discovery of the discotic liquid crystal was made in 1977, and the interest has increased very recently, the demand has not always been sufficiently answered.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a discotic compound having a triphenylamine derivative and a phenylcarbazole derivative as substituents.

[0007]

As a result of intensive studies, the present inventor has found that the object of the present invention can be achieved as follows. (1) A compound represented by the general formula (1). General formula (1)

[0008]

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In the formula, L represents a divalent group. Q represents an optionally substituted diphenylaminophenyl group or 9-
Represents a carbazolylphenyl group. (2) In the general formula (1), L is composed of methylene alone or methylene and an oxygen atom, or L composed of methylene alone or a methylene containing an amide bond or methylene and an oxygen atom (the above (1) Described)
Compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Examples of the divalent group represented by L in the general formula (1) include an alkylene group (eg, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene), an alkyleneoxy group (eg, ethyleneoxy, propylene) Oxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, nonyleneoxy), an arylene group (for example, 1,4-phenylene, 2-methyl-
1,4-phenylene, 2-methoxy-1,4-phenylene, 1,4′-biphenylene), combinations of the above groups, and divalent groups having up to 0 or 25 carbon atoms in combination with the above groups. Groups [for example, -O-, -S-,-
C (O)-, -OC (O)-, -S (C = S)-,-
OC (O) -O-, -C (O) -OC (O)-,-
C (O) NR ^0- , -NR ^0- , -NR ⁰ (O) NR-
(R ⁰ is a hydrogen atom or a lower alkyl group).

Preferably, an alkylene group, an alkyleneoxy group, or a group in which a methylene group is replaced by an oxygen atom or an amide group. More preferably, they are those having 4 to 10 atoms, and furthermore, an alkyleneoxy group.

The substituent in the optionally substituted diphenylaminophenyl group or 9-carbazolylphenyl group represented by Q in the general formula (1) includes:
For example, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, halogen atom (fluorine, chlorine, bromine), alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, Thiol group, amino group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylcarbonylthio group, arylcarbonylthio group, alkylsulfonylthio group, arylsulfonylthio group, alkylcarbonylamino group ,
Examples include an arylcarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a carboxy group, and a sulfo group, and the alkyl group and the aryl group may be substituted. Further, the groups substituted at a plurality of positions may be bonded to each other to form a ring such as a cyclohexene ring and a benzene ring.

The alkyl group preferably has 1 to 24, more preferably 1 to 12, carbon atoms. More specifically, for example, an alkyl group (eg, methyl, ethyl, n-pentyl, n-hexyl, n-heptyl, n-
Octyl, n-nonyl, n-decyl, n-undecyl,
n-dodecyl, i-propyl, i-butyl, sec-butyl, t-amyl, 2-ethylhexyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-
Methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2-n-butoxyethyl, 2-ethoxyethyl, 2- (2-ethoxyethoxy) ethyl, 3-methoxypropyl, 3-ethoxy Propyl, 3-n-propyloxypropyl, 2-methylbutyloxymethyl).

The aryl group has preferably 6 to 24 carbon atoms, more preferably 6 to 14 carbon atoms. More specifically, for example, a phenyl group (for example, phenyl, 2-
Tolyl, 3-tolyl, 4-tolyl, 2-anisyl, 3-
Anisyl, 4-anisyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), and a naphthyl group (for example, 1-naphthyl, 2-naphthyl) are exemplified. Further, the aryl group may be a heteroaromatic group such as a pyridyl group, a pyrimidyl group, a thiazolyl group, and an oxazolyl group.

Hereinafter, specific examples of the compound used in the present invention will be shown. However, the scope of the present invention is not limited only to these.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The compound of the present invention can be synthesized, for example, by the following method. That is, a method of introducing a group of L or less of the general formula (1) into the triphenylene skeleton, or introducing a group of L or less of the general formula (1) at the 1, 2 position of the benzene ring, followed by oxidative trimerization. How to In the case of the present invention, the former is preferred. Solvents that can be used in the synthesis of the compounds of the present invention include, for example, N, N-dimethylformamide (D
MF) and dimethylsulfoxide (DMSO) to a relatively low-polarity solvent such as aromatic compounds such as o-dichlorobenzene and xylene and aliphatic compounds such as decalin. DMF, DM
High-boiling solvents such as SO, o-dichlorobenzene and decalin are preferred, and mixed solvents can also be used. The reaction temperature at the time of synthesis of the compound of the present invention is preferably 50 ° C to 300 ° C, more preferably 100 ° C to 250 ° C.
It is.

[0023]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Synthesis of Compound 1) A solution consisting of 2.29 g (20 mmol) of methanesulfonyl chloride and 10 ml of tetrahydrofuran (THF) cooled to 0 ° C. was added with stirring to a solution of 5.78 g (20
mmol) 4-carboxytriphenylamine;
41 ml of diisopropylethylamine and 40 ml
Was added dropwise at 5 ° C. or lower. After completion of the dropwise addition, the mixture was stirred for 20 minutes under ice cooling, and then 3.41 ml of diisopropylethylamine, 0.24 g (2 mmol)
4- (N, N-dimethylamino) pyridine, 1.67
A suspension consisting of g (2 mmol) of 2,3,6,7,10,11-hexakis- (5-aminopentyloxy) triphenylene and 30 ml of THF was added successively.
Thereafter, stirring was continued at room temperature for 8 hours, and the mixture was further left overnight. The reaction mixture was poured into ice water, and the supernatant was removed by decantation. The residue was subjected to silica gel chromatography (eluent: dichloromethane / methanol = 49/1 to 49/1).
24/1) to give the desired product. Yield 1.18 g
(Yield 24.0%)

¹ H-NMR (δ ppm in DMSO
_{-D 6): 1.59 (m,} 24H), 1.83 (m, 12
H), 3.30 (m, 12H), 4.22 (m, 12
H), 6.89 (d, 12H), 7.05 (d, 24
H), 7.10 (d, 12H), 7.31 (t, 24
H), 7.72 (d, 12H), 7.98 (s, 6
H), 8.31 (t, 6H)

Example 2 (Synthesis of Compound 9) 2.14 g (1 mmol) of 2,3,6,7,10,1
1-hexakis- [6- (4-iodophenyloxy)
Hexyloxy] triphenylene, 5.07 g (30 m
mol) of diphenylamine, 6.86 g (36 mmol)
1) cuprous iodide and 8.28 g (60 mmol)
To potassium carbonate (anhydrous) was added 100 ml of o-dichlorobenzene, and the mixture was refluxed and stirred for 24 hours. The reaction mixture is
After cooling to room temperature, the mixture was filtered, the filtrate was concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: dichloromethane / hexane = 8/2 to 10/0) to obtain the desired product. 1.53 g (64.2% yield)

¹ H-NMR (δ ppm in CDC
l ₃ ): 1.67 (m, 24H), 1.86 (m, 12
H), 2.00 (m, 12H), 3.97 (t, 12
H), 4.25 (t, 12H), 6.81 (d, 12
H), 6.92 (t, 12H), 7.01 (d, 24
H), 7.00 (d, 12H), 7.15 (t, 24
H), 7.83 (s, 6H)

Example 3 (Synthesis of Compound 25) 1.07 g (0.5 mmol) of 2,3,6,7,1
0,11-hexakis- [6- (4-iodophenyloxy) hexyloxy] triphenylene, 2.51 g
(15 mmol) of carbazole, 3.43 g (18 m
mol) of cuprous iodide and 4.14 g (30 mmol)
50 ml of o-dichlorobenzene was added to 1) potassium carbonate (anhydrous), and the mixture was stirred under reflux for 24 hours. The reaction mixture was allowed to cool to room temperature, filtered, and the filtrate was concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: dichloromethane / hexane = 8/2) to obtain the desired product. 1.10 g (92.8% yield)

¹ H-NMR (δ ppm in CDC
l ₃ ): 1.68 (m, 24H), 1.92 (m, 12
H), 2.04 (m, 12H), 4.04 (t, 12
H), 4.27 (t, 12H), 7.04 (d, 12
H), 7.20-7.45 (m, 48H), 7.93
(S, 6H), 8.12 (d, 12H)

Reference Example (Observation of Liquid Crystallinity) A powder of Compound 9 was placed on a slide glass, and a phase change was observed with a polarizing microscope while heating on a Mettler FP82HT hot stage. The liquid crystal phase was shown in the range of 103 to 113 ° C.

[0030]

The compounds of the present invention show liquid crystallinity and are useful as novel compounds as well as liquid crystal compounds.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // G02F 1/13 500 G02F 1/13 500

Claims (2)

[Claims] 1. A compound represented by the general formula (1). General formula (1) In the formula, L represents a divalent group. Q represents an optionally substituted diphenylaminophenyl group or 9-carbazolylphenyl group. 2. In the general formula (1), L is composed of methylene alone or methylene and an oxygen atom, or L is composed of methylene containing an amide bond alone or methylene and an oxygen atom. A compound as described.