JP2001335526A - Discotic liquid crystal compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new discotic liquid crystal compound useful for a new material of discotic liquid crystals having various functions. SOLUTION: This new discotic liquid crystal compound is shown by the general formula (I) (wherein, A is a discotic liquid-crystalline mesogenic group; R is a 1-100C straight-chain or branched alkyl, and at least one methylene group in the above alkyl group may be substituted with O, CO, S, CH=CH or C≡C, and also the hydrogen atom(s) in the above alkyl group may be substituted with fluorine atom(s); and n is an integer of 1-8).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel discotic liquid crystal compound and a method for producing the same.

[0002]

2. Description of the Related Art The discotic liquid crystal phase was developed in 1977 by S.M. (“Prana” 9 , 471 (1977)), a liquid crystal phase discovered by Chandrasekhar et al. For example, by the authors,
c Liquid Crystals ”and“ Re
p. Prog. Phys. " 53 (1990) 57,
Alternatively, as described in Shunsuke Takenaka entitled “Design and Synthesis of Discotic Liquid Crystal Molecules”, edited by the Chemical Society of Japan, “Quarterly Review of Chemistry,” Vol. 22, p. It is found in compounds with multiple chains.

The types of the compounds can be classified mainly according to the structure of the core. Derivatives of 6-substituted benzene and 3-substituted benzene, phthalocyanine and porphyrin derivatives, triphenylene, tolcene, pyrylium derivatives, and tribenzocyclononene derivatives Azacrown derivatives, cyclohexane derivatives and the like.

Some reports have been made in the past suggesting application to devices based on the structural characteristics of discotic liquid crystals. In systems with conjugated pi electrons, such as phthalocyanine and triphenylene, the application of electron (or hole) channels (Pieocki et a
l. : “J. Am. Chem. Soc.” 1982, 1
04, pp5245), when the core is a ring like azacrown, an application of a molecular channel in which a molecule selectively passes through a central void portion (“J. Chem. Soc., Ch.
em. Commun. ", 1985, 1794," J.
Chem. Soc. Chem. Commun. ", 1
995, 117, 9957) and the like.

However, discotic liquid crystals are more difficult to synthesize than rod-like liquid crystals, and many compounds having functional groups for modifying various structures are not known.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such prior art, and a novel discotic liquid crystal compound which is a useful derivative of a discotic liquid crystal having various functions and a novel compound thereof. It is intended to provide a manufacturing method.

[0007]

That is, the present invention is a discotic liquid crystal compound represented by the following general formula (I).

[0008]

Embedded image

Wherein A represents a discotic liquid crystalline mesogen group. R is a linear or branched alkyl group having 1 to 100 carbon atoms, and at least one methylene group in the alkyl group The groups are -O-, -CO-, -S-, -CH
= CH- or -C≡C-. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. n shows the integer of 1-8.

[0010]

Embedded image May be an optically active group. )

It is preferred that A of the compound represented by the general formula (I) is a benzene ring or a triphenylene ring. It is preferable that the compound represented by the general formula (I) is an optically active compound.

Further, the present invention provides a compound represented by the following general formula (II):

[0013]

Embedded image (Wherein, A represents a discotic liquid crystalline mesogen group; n represents an integer of 1 to 8);
The following general formula (III)

[0014]

Embedded image (Wherein, R is a linear or branched alkyl group having 1 to 100 carbon atoms, and one or more methylene groups in the alkyl group are -O-, -CO-, -S-, -CH = CH
— Or —C≡C— may be substituted. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. A method for producing a discotic liquid crystal compound represented by the following general formula (I), comprising reacting a compound represented by the formula (1) in the presence of a base.

[0015]

Embedded image (In the formula, A, R and n represent the same as above.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The discotic liquid crystal compound of the present invention is characterized by comprising a compound represented by the following general formula (I).

[0017]

Embedded image

In the general formula (I), A represents a discotic liquid crystalline mesogen group. Specific examples of the discotic liquid crystalline mesogen group include a benzene ring, a triphenylene ring, a tolcene ring, a pyrene ring, and a tricycloquinazoline ring. From the viewpoint of planarity important for liquid crystallinity, A represents a benzene ring or a triphenylene ring. Compounds that are rings are preferred. Further, a compound having a triphenylene ring is preferable.

R is a linear or branched alkyl group having 1 to 100 carbon atoms, and one or more methylene groups in the alkyl group are -O-, -CO-, -S-,- CH =
CH- or -C≡C- may be substituted. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom.

N represents an integer of 1 to 8. Also,

[0021]

Embedded image May be an optically active group, and the compound represented by the general formula (I) may be an optically active compound.

The compound of the present invention has a discotic liquid crystalline mesogen group and further has six useful hydroxyl groups as functional groups. A compound having a hydroxyl group at a terminal of a side chain (“Langmuir” 9,1561, 1993) is known, but a compound having a hydroxyl group near a mesogen group is not known. Having these hydroxyl groups enables conversion to other useful functional groups or bonding with other compounds. It is also easy to polymerize by a crosslinking reaction.

Hereinafter, specific structural formulas of the compounds of the present invention are shown in Tables 1 to 12. However, the present invention is not limited only to these.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

[0029]

[Table 6]

[0030]

[Table 7]

[0031]

[Table 8]

[0032]

[Table 9]

[0033]

[Table 10]

[0034]

[Table 11]

[0035]

[Table 12]

Next, the method for producing the discotic liquid crystal compound represented by the above general formula (I) of the present invention is represented by the following general formula (II)

[0037]

Embedded image (Wherein, A represents a discotic liquid crystalline mesogen group; n represents an integer of 1 to 8);
General formula (III)

[0038]

Embedded image

Wherein R is a linear or branched alkyl group having 1 to 100 carbon atoms, and one or more methylene groups in the alkyl group are -O-, -CO-,- S-,
—CH ＝ CH— or —C≡C— may be substituted. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. ) Is reacted in the presence of a base.

Further, the general synthesis method of the present invention will be described by taking as an example the case where the mengen group shown in the following reaction formula is triphenylene.

[0041]

Embedded image (In the formula, R represents the same as described above.)

The above reaction is carried out by adding hexahydroxytriphenylene (II ') and a base to an organic solvent, adding the compound (III) dropwise thereto, and stirring. The reaction temperature depends on the boiling point of the solvent used, but is preferably from 60C to 90C.
The reaction time needs at least 3 hours or more to complete the reaction.

The organic solvent used in the reaction is not particularly restricted but includes, for example, toluene, ether, tetrahydrofuran, N, N'-dimethylformamide, methanol,
Preference is given to ethanol, butanol and the like.

As the base used in the reaction, triethylamine, pyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and the like are preferable. The amount of the base to be added is preferably 6 to 7 molar equivalents to hexahydroxytriphenylene.

The amount of the compound (III) is also 6-fold mole to 7-fold with respect to hexahydroxytriphenylene.
Double molar equivalents are preferred. After completion of the reaction, the solvent is distilled off as it is, and then purified by column chromatography or recrystallization to obtain the desired discotic liquid crystal compound (I ').
Can be obtained.

In some cases, after addition of an acidic aqueous solution such as hydrochloric acid, extraction with an organic solvent, drying and purification can be performed. When an optically active compound of R-form or S-form is used as the compound (III), it can be easily converted to an optically active form.

[0047]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 Production of 2,3,6,7,10,11-hexa (2-hydroxy-3-butyloxypropyloxy) triphenylene (Exemplary Compound No. I-4)

In a reaction vessel, 15 ml of dry ethanol and 5.6 g (40.5 mmol) of potassium carbonate were put, and 2.0 g (6.17 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene was placed in a water bath. Was added and stirred at 70 ° C. for 10 minutes. Thereafter, a mixture of 4.8 g (36.9 mmol) of butyl glycidyl ether and 20 ml of dry ethanol was added dropwise, and the mixture was stirred at 80 ° C. for 6 hours. After completion of the reaction, 40 ml of 3N-HCl was added to make the mixture acidic, and the mixture was extracted five times with chloroform. After the extract was washed with water, anhydrous sodium sulfate was added and dried. After the solvent was distilled off, purification was carried out twice by silica gel column chromatography (elution solvent: chloroform / ethanol = 50/1), and 2,3,6,7,10,11-hexa (2-hydroxy-3- Butyloxypropyloxy)
2.64 g (2.39 mmol) of triphenylene were obtained. 39% yield

FIG. 1 shows 2,3,6 produced in Example 1.
1 shows an NMR chart of 7,10,11-hexa (2-hydroxy-3-butyloxypropyloxy) triphenylene.

Example 2 Optically active 2,3,6,7,10,11-hexa (3-hydroxy-1,5,8,11,14,17-hexaoxaoctadecyl) triphenylene (Exemplified Compound No. I
Production of -21)

In a reaction vessel, 50 ml of dry ethanol and 16.6 g (120 mmol) of potassium carbonate were added, and 4.6 g (14.3 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene was added thereto in a water bath. And stirred at 70 ° C. for 30 minutes. Then, the optical activity 3,
6,9,12-tetraoxatridecyl glycidyl ether (26.4 g, 100 mmol) and dry ethanol 5
0 ml of the mixture was added dropwise, and the mixture was stirred at 80 ° C. for 12 hours.
After completion of the reaction, 100 ml of 3N-HCl was added to make the mixture acidic, and the mixture was extracted five times with chloroform. After the extract was washed with water, anhydrous sodium sulfate was added and dried. After the solvent was distilled off, purification was carried out twice by silica gel column chromatography (elution solvent: chloroform / ethanol = 10/1), and the optically active 2,3,6,7,10,11-hexa (3-hydroxy- 1,5,8,11,14,17
-Hexaoxaoctadecyl) triphenylene 13.8
g (7.2 mmol) were obtained. Yield 50%

FIG. 2 shows the optically active 2, produced in Example 2.
3,6,7,10,11-hexa (3-hydroxy-
1 shows an NMR chart of (1,5,8,11,14,17-hexaoxaoctadecyl) triphenylene.

Example 3 2,3,6,7,10,11-hexa (2-hydroxydecyloxy) triphenylene (Exemplified Compound No. I-
133) Manufacturing

A reaction vessel was charged with 100 ml of dry ethanol and 28 g (202.5 mmol) of potassium carbonate, and 10 g (30.9 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene was added thereto in a water bath. Stirred at C for 60 minutes. Thereafter, a mixed solution of 28.8 g (184.5 mmol) of 1,2-epoxydecane and 100 ml of dry ethanol was added dropwise, and the mixture was stirred at 80 ° C. for 24 hours. After the reaction was completed, 200 ml of 3N-HCl was added to make the mixture acidic, and the mixture was extracted five times with chloroform. After the extract was washed with water, anhydrous sodium sulfate was added and dried. After distilling off the solvent, silica gel column chromatography (elution solvent: chloroform / ethanol = 50)
/ 1) twice to purify and purify 2,3,6,7,10,1
22.8 g (18.1 mmol) of 1-hexa (2-hydroxydecyloxy) triphenylene were obtained. Yield 59
%

FIG. 3 shows 2,3,6 produced in Example 3.
1 shows an NMR chart of 7,10,11-hexa (2-hydroxydecyloxy) triphenylene.

[0057]

As described above, according to the present invention, it is possible to provide a novel discotic liquid crystal compound which is a useful derivative of a discotic liquid crystal having various functions and a method for producing the same.

[Brief description of the drawings]

FIG. 1 shows 2,3,6,7,10,1 produced in Example 1.
1 shows an NMR chart of 1-hexa (2-hydroxy-3-butyloxypropyloxy) triphenylene.

FIG. 2 shows the optical activity 2,3,6,7,
10,11-hexa (3-hydroxy-1,5,8,1
1 shows an NMR chart of (1,14,17-hexaoxaoctadecyl) triphenylene.

FIG. 3 shows 2,3,6,7,10,1 produced in Example 3
1 shows an NMR chart of 1-hexa (2-hydroxydecyloxy) triphenylene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4H006 AA01 AA02 AB64 AC43 BA02 BA28 BA29 BA32 BA51 GN06 GP03 GP10 4H027 BA08 CA03 CA08 DM03 DM08 4H039 CA61 CF90

Claims (5)

[Claims] 1. A discotic liquid crystal compound represented by the following general formula (I). Embedded image (In the formula, A represents a discotic liquid crystalline mesogen group. R is a linear or branched alkyl group having 1 to 100 carbon atoms, and one or more methylene groups in the alkyl group are- O-, -CO-, -S-, -CH = CH- or -C≡C- may be substituted, and a hydrogen atom in the alkyl group may be substituted by a fluorine atom. n represents an integer of 1 to 8. May be an optically active group. ) 2. A compound of the formula (I)
The discotic liquid crystal compound according to claim 1, wherein is a benzene ring or a triphenylene ring. 3. A compound of the formula (I)
The discotic liquid crystal compound according to claim 1, wherein is a triphenylene ring. 4. The discotic liquid crystal compound according to claim 1, wherein the compound represented by the general formula (I) is an optically active compound. 5. The following general formula (II): (Wherein, A represents a discotic liquid crystalline mesogen group; n represents an integer of 1 to 8);
The following general formula (III): (Wherein, R is a linear or branched alkyl group having 1 to 100 carbon atoms, and one or more methylene groups in the alkyl group are -O-, -CO-, -S-, -CH = CH
— Or —C≡C— may be substituted. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. A method for producing a discotic liquid crystal compound represented by the following general formula (I), wherein the compound represented by the formula (I) is reacted in the presence of a base. Embedded image (In the formula, A, R and n represent the same as above.)