JP2001106647A - New disklike compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new disklike compound having at least one fluorine atom. SOLUTION: This disklike compound is substituted by a substituent group containing an alkyl group having at least one fluorine atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel discotic compound.

[0002]

2. Description of the Related Art Discotic compounds, which are compounds having a discotic shape, are useful, for example, as discotic liquid crystal compounds. Discotic liquid crystal compounds are attracting attention for their usefulness as electronically functional materials due to their conduction anisotropy and hole mobility, and there are also research examples of electroluminescent devices. For these, reference can be made to the following documents, for example. N. Boden et al.,
J. Chem. Phys., 98 (7), 5920-5931, D. Adam et al., Natur
e, 371, 141-143 (1994), V. Stmpflen et al., Adv. Mater.,
1997, 9 (1), 48-52, S. Tanaka et al., Chem. Lett., 1998, 975.
-976.

[0003] Further, application to an optically anisotropic material utilizing the negative refractive index anisotropy of a discotic liquid crystal compound has been performed. For this, the following documents can be referred to, for example. B. Mourey et al., Mol. Cryst. Liq.
Cryst., 84, 193 (1982), H. Mori et al., Jpn. J. Appl. Phys.,
36,143 (1997), Ken Kawata et al., Liquid Crystal, 1 (1), 45-56 (199
7).

[0004] As described above, discotic liquid crystal compounds, which are discotic compounds, are of interest for their usefulness. However, as compared with rod-shaped liquid crystals widely used in liquid crystal displays, discotic liquid crystal compounds which are not practically used other than the above-mentioned optically anisotropic materials are still few. In a rod-like liquid crystal, the introduction of fluorine atoms produces interesting effects such as a large change in dielectric anisotropy. However, among discotic liquid crystal compounds, compounds into which fluorine atoms have been introduced are not sufficiently known. Fluorine atoms have a high electronegativity, and their introduction is expected to lower the energy level. When considered as an electronically functional material, it is expected to exhibit not only functions as a hole transporting agent but also functions as an electron transporting agent.

[0005]

Accordingly, an object of the present invention is to provide a novel discotic compound having a fluorine atom.

[0006]

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 discotic compound which is substituted with a substituent containing an alkyl group having at least one fluorine atom. (2) The discotic compound according to (1), wherein the substituent is an alkoxy group. (3) The discotic compound according to claim 1 or 2, wherein the discotic core of the discotic compound is a triphenylene derivative. (4) The discotic compound is a compound represented by the following general formula (1), (1), (2) or (3)
A discotic compound as described.

[0007]

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In the formula, each of R ^a , R ^b and R ^c may be the same or different and represents a hydrogen atom, an alkyl group or an acyl group. However, at least one of R ^a , R ^b , and R ^c
One is an alkyl group having at least one fluorine atom.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The discotic compound in the present invention has, for example, a discotic structure as a core (so-called core),
It refers to a compound in which, for example, side chains are radially connected from the core. As a definition of a disc-shaped core, for example,
No. 111240 can be mentioned. In addition, examples of the core included therein include those described in the above specification.

More specific examples include, for example, benzene derivatives, triphenylene derivatives, truxene derivatives, phthalocyanine derivatives, porphyrin derivatives, anthracene derivatives, azacrown derivatives, cyclohexane derivatives, β-diketone metal complex derivatives, hexaethynylbenzene derivatives, Dibenzopyrene derivatives, coronene derivatives and phenylacetylene macrocycles. The discotic core is preferably a triphenylene derivative, a truxene derivative, or a phenylacetylene macrocycle, and more preferably a triphenylene derivative.

As the alkyl group having a fluorine atom in the present invention, a catalog of Daikin Chemicals Sales Co., Ltd. can be referred to, for example, trifluoromethyl,
2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro -2-propyl, 2,2,3,3,4,4,4-heptafluorobutyl.

The alkyl group having a fluorine atom in the present invention is preferably an alkyl group having 3 or more (preferably 10 or less) fluorine atoms, and the alkyl portion preferably has 1 to 20 carbon atoms. Is more preferably 1 or more and 8 or less, and particularly preferably 2 or more and 6 or less. The compound of the present invention may be substituted with the following substituents in addition to the alkyl group having a fluorine atom. Examples of the substituent include C.I. Hansch, A .; L
eo, R.E. W. Taft, Chemical Review Magazine (Ch
em. Rev .. 1991, 91, 165-195
Pages (American Chemical Society). The following are typical examples.

A substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, Methoxyethoxyethyl, 2
-Hydroxyethyl, 3-hydroxypropyl), alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group or n-butoxy group), alkenyl group, alkynyl group, aryl group (for example, phenyl, 1-naphthyl,
2-naphthyl, tolyl), halogen atom, cyano group, nitro group, hydroxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, alkylamino group, arylamino group, carbonamido group , Sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, acyl group, oxycarbonyl group, carbamoyl group,
Carboalkoxy group, sulfonyl group, sulfinyl group,
An oxysulfinyl group or a sulfamoyl group, a heterocyclic ring (for example, pyridyl group, pyrimidyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, thiazolyl group,
Imidazolyl group, oxazolyl group, thiadialyl group, oxadiazolyl group, quinolyl group, isoquinolyl group, tetrahydrofuryl group [these substituents are collectively referred to as V in the present invention] and combinations thereof.
A substituent containing an alkyl group having a fluorine atom is bonded to the discotic core via a carbon atom or the like of the core, and the substituent is preferably an alkoxy group or an acyloxy group, more preferably an alkoxy group. is there. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms, methoxy group, ethoxy group, n-propoxy, n -Butoxy group, n-pentyloxy group, n-hexyloxy group and the like. These alkoxy groups may have a substituent, and examples of the substituent include V. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group, and these groups may be further substituted by V or the like. R ^a , R ^b and R ^c may be the same or different and each represents a hydrogen atom, an alkyl group or an acyl group. R
^The alkyl groups represented by ^a , R ^b , and R ^c include the substituted or unsubstituted alkyl groups described in the above V, and the acyl group includes an acetyl group, a benzoyl group, and the like. The group may be further substituted by V or the like. Preferably, R ^a , R ^b , and R ^c are alkyl groups having a fluorine atom, and more preferably,
This is the case where R ^a , R ^b , and R ^c are alkyl groups having the same fluorine atom.

Hereinafter, specific examples of the compound of the present invention will be described, but the scope of the present invention is not limited thereto.

[0015]

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[0016]

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[0017]

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These compounds can be generally synthesized with reference to the above-mentioned documents and the documents described therein.

[0019]

The present invention will be described below in more detail with reference to the following examples.

Example 1 (Synthesis of Compound 1) Synthesis of 2,3,6,7,10,11-hexa (2,2,2-trifluoroethoxy) triphenylene. 972 mg (3 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene, 4.56 g of 2,2,2-trifluoroethyl-4-toluenesulfonate
(18 mmol) and 2.48 g (18 mmol) of potassium carbonate were added with 50 ml of N, N-dimethylacetamide, and the mixture was heated with stirring at 120 ° C. for 30 minutes. 2,
4.56 g (18 mmol) of 2,2-trifluoroethyl-4-toluenesulfonate and potassium carbonate
48 g (18 mmol) was further added, followed by heating and stirring for 3 hours. After cooling to room temperature, the reaction mixture is
The mixture was poured into 0 ml of ice water and extracted with ethyl acetate.
After washing the ethyl acetate layer with water, it was dried over anhydrous sodium sulfate. After the desiccant was filtered off, the solvent was distilled off under reduced pressure, and methylene chloride was added to the residue. The precipitated crystals were collected by filtration, and further recrystallized with a mixed solvent of ethyl acetate / methanol using activated carbon. The desired product was obtained as white crystals. Yield 56
0 mg (22.9% yield)

¹ H-NMR (δin DMSO-d ₆ ):
5.05 (q, 12H), 8.30 (s, 6H) FABMS: m / z = 817

Phase transition temperature: Differential scanning calorimetry (DSC)
And from 251.4 ° C. to 25
A liquid crystal phase was observed between 8.7 ° C.

Example 2 (Synthesis of Compound 2) 2,3,6,7,10,11-hexa (2,2,3,3
Synthesis of (tetrafluoropropoxy) triphenylene. 2,2,2-trifluoroethyl-4-toluenesulfonate is converted to 2,2,3,3-tetrafluoropropyl-4
-The same reaction was carried out in place of chlorobenzenesulfonate. Purification was performed by silica gel column chromatography (eluent: hexane / ethyl acetate = 8/2). The desired product was obtained as white crystals. Melting point 228.1 ° C

¹ H-NMR (δinDMSO-d):
4.67 (t, 12H) 6.20 (t, 12H), 8.
00 (s, 6H) FABMS: m / z = 11009

Example 3 (Comparison of Oxidation Potential) Oxidation potential was measured to examine the degree of decrease in energy level. The results are shown in Table 1.
The values shown are those measured on an Ag / AgCl electrode (supporting electrolyte: tetrabutylammonium perchlorate) in an N, N-dimethylformamide solution.

[0026]

[Table 1]

[0027]

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Compared with the comparative compound A, the compound of the present invention clearly shows a large noble potential, and the energy level was reduced as expected.

[0029]

According to the present invention, a novel liquid crystalline compound and a compound having a reduced energy level can be obtained.

Claims (4)

[Claims] 1. A discotic compound which is substituted by a substituent containing an alkyl group having at least one fluorine atom. 2. The discotic compound according to claim 1, wherein the substituent is an alkoxy group. 3. The discotic compound according to claim 1, wherein the discotic core of the discotic compound is a triphenylene derivative. 4. The compound according to claim 1, wherein the discotic compound is a compound represented by the following general formula (1).
A discotic compound as described. Embedded image In the formula, R ^a , R ^b , and R ^c may be the same or different and each represents a hydrogen atom, an alkyl group, or an acyl group.
However, at least one of R ^a , R ^b , and R ^c is an alkyl group having at least one fluorine atom.