JP2003096015A - Cyclic liquid crystalline composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new cyclic liquid crystalline composition for an ionic conductive material. SOLUTION: The new cyclic liquid crystalline compound having a calixarene within its molecular core and a cone shape molecule shown by the formula below (wherein, R is Cn H2n+1 ; and n is an integer of 5 to 23) is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel liquid crystal material having both thermotropic liquid crystallinity and lyotropic liquid crystallinity, and a novel calix synthesized as a novel liquid crystalline compound toward an ionic conductor by manifesting a tubular columnar liquid crystal phase. It relates to arene derivatives.

[0002]

DISCLOSURE OF THE INVENTION The present invention relates to a novel liquid crystal material having both thermotropic liquid crystallinity and lyotropic liquid crystallinity, and a novel ring-shaped liquid crystal for an ion conductor due to manifestation of a tubular columnar liquid crystal phase. It aims at providing a sex composition.

Conventionally, calixarene having various ring sizes has been synthesized, but this is because the selectivity of the metal ion to be captured is obtained depending on the ring size. It has also been proved that these metal ion recognitions are made in solution.

However, from the viewpoint of ion transport, the functions of recognizing and incorporating these selective metal ions are indispensable for the calixarene to aggregate to construct a route for metal ion transport. For that reason, attempts to synthesize liquid crystalline compounds having a calixarene in the center of the structure have been continued until now.

Further, some known examples of liquid crystals having a calixarene in the molecular skeleton are known.
All of them have thermotropic liquid crystallinity, and no compound having lyotropic liquid crystallinity at the same time has been found. Considering the application to an ionic conductor, not only is large molecular motion in the liquid crystal state advantageous, and the direction in which the ions easily move is determined according to the orientation of the molecule, which is convenient, and the liquid crystal phase in a liquid such as a solvent The lyotropic properties exhibited also favor the presence of ions.

Therefore, a liquid crystal compound having a calixarene at the center of its structure, and further a liquid crystal compound satisfying both the thermotropic liquid crystal property and the lyotropic liquid crystal property at the same time have been earnestly desired.

[0007]

The inventors of the present invention have conducted extensive studies in view of the above-mentioned problems, and as a result, the results are shown in FIG.
Having a calixarene in the molecular core (R = C _n H _{2n + 1} ;
n is an integer of 5 to 23), and a new liquid crystal compound having a cone-shaped molecular shape was found. The liquid crystalline compound has a calixarene part and a phenyl group having an alkyl long chain as C
A calixarene liquid crystal compound having such a structure, which is connected by a ≡C triple bond, has not been reported yet, and was first discovered by the present inventors.

It has also been found that the novel liquid crystalline compounds exhibit both temperature-dependent (thermotropic) and concentration-dependent (lyotropic) liquid crystallinity.

Further, since the molecules are in a laminated state such that caps are stacked in the columnar phase which develops,
The inventors have found that the liquid crystalline compound has a column liquid crystal phase, and have completed the present invention.

The present invention relates to novel calixarene derivatives as shown below. Item 1. Chemical formula (1);

[0011]

[Chemical 2]

A liquid crystalline compound having a chemical structure represented by the formula (wherein R = C _n H _{2n + 1} ; n is an integer of 5 to 23). Item 2. The liquid crystalline compound according to claim 1, which has a thermotropic liquid crystalline property and a lyotropic liquid crystalline property. Item 3. The liquid crystalline compound according to claim 1, which has a liquid crystal phase having a column structure. Item 4. The liquid crystalline compound according to claim 1, wherein R is an alkyl chain having 5 to 23 carbon atoms.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention has the general formula (1):

[0014]

[Chemical 3]

As shown by the formula (R = C _n H _{2n + 1} ; n is an integer of 5 to 23), it has a calixarene in the molecular core and has a cone-shaped molecular shape.

R in the above general formula is the same or different and
= C _n H _{2n + 1} (n is an integer of 5 to 23).

The number of carbon atoms of these alkyl groups is 5 to 23 carbon atoms, preferably 10 to 23 carbon atoms, and more preferably 12 carbon atoms for the purpose of maintaining the liquid crystallinity of the compound.
-16 are mentioned.

For example, as shown in FIG. 2, the liquid crystal compound of the present invention has a column liquid crystal phase because the molecules are in a laminated state such that the caps are overlapped in the columnar phase that develops ( M +: represents a metal cation).

The liquid crystalline compound of the present invention exhibits a temperature-dependent (thermotropic) liquid crystallinity which takes a liquid crystal state as a result of a phase transition accompanying a temperature change. In addition, it exhibits a concentration-dependent (lyotropic) liquid crystallinity that becomes a liquid crystal at room temperature in a certain concentration range in the presence of an ordinary organic solvent such as hexane or acetone.
The compounds having both thermotropic and lyotropic liquid crystallinity have not been known so far.

Further, the liquid crystal phase represented by this compound has a column structure formed by stacking cone type molecules,
In addition to being deeply involved in the expression of one function of optical and electronic properties such as the switching function of electrical characteristics using the response of the column structure to an external field such as an electric field, high charge transfer efficiency derived from the column structure, various optical waveguide controllability, etc. The various physical properties of p can open the way for new applications of liquid crystal materials in the future.

[0021]

EXAMPLES The contents of the present invention will be described more specifically below with reference to examples, but the present invention is not limited thereto.

Example 1 Synthesis of hexadecyloxy derivative (C16) (1) Synthesis of p-tetra-tert-butyltetrahydroxycalix [4] arene 21 ml of formaldehyde (37% aqueous solution), p-te
33 g of rt-butylphenol and 0.6 g of sodium hydroxide were heated at 110-120 ° C. for 2 hours. After allowing the reaction product to cool at room temperature, 100 ml of diphenyl ether
Dissolved in. The mixture was heated to the reflux temperature while flowing nitrogen gas, and then refluxed by heating at 245 ° C. for 2 hours. After allowing to cool to room temperature, 150 ml of ethyl acetate was added to precipitate a solid. After leaving it as such for 14 hours, suction filtration was performed to separate the precipitate. The solid was washed twice with ethyl acetate,
It was washed once with acetic acid and twice with water. Boiled toluene 5
After dissolving the solid in 00 ml, the solvent amount was distilled in half and the mixture was allowed to cool to precipitate white crystals. The white crystals were filtered and dried to obtain 15 g of the desired product.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 9.6 (s, 4
H, ArO H ), 7.17 (s, 8H, Ar H ), 4.30 (br d, 4H, Ar-C
H ₂ ), 3.55 (br d, 4H, Ar-C H ₂ ), 1.26 (s, 36H, -C (C
H _{3) 3).}

(2) Tetrahydroxycalix [4]
6.65 g of calixarene synthesized in the above (1),
7 g of aluminum chloride and 4.5 g of phenol were dissolved in 60 ml of toluene and stirred at room temperature for 1 hour. After adding 125 ml of concentrated hydrochloric acid to the reaction mixture to terminate the reaction,
The product was extracted with toluene. After distilling off the solvent to some extent, 20 ml of methanol was added and the precipitated white solid was filtered off. Recrystallization from a mixed solution of chloroform and methanol gave 3 g of the desired product.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 10.2 (s, 4
H, ArO H ), 7.04 (d, 8H, Ar H ), 6.72 (t, 4H, Ar H ), 4.26
(brd, 4H, Ar-C H ₂ ), 3.51 (br d, 4H, Ar-C H ₂ ).

(3) Synthesis of corn-type tetrapropoxycalix [4] arene 2.3 g of calixarene synthesized in the above (2) was melted in 50 ml of dimethylformamide and then slowly stirred under a nitrogen gas stream with stirring. To the mixture was added 2.4 g of sodium hydride. After stirring for 5 minutes, 8 g of propyl bromide was added, and the mixture was stirred overnight at room temperature. First, methanol
Excess sodium hydride was then treated by adding water.
After filtering the reaction mixture, the solid obtained was purified by flushing a column of silica gel with a mixed solution of hexane and methylene chloride. As a result, 1.4 g of white crystals were obtained.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 6.57 (s, 8
H, Ar H ), 4.44 (d, 4H, Ar-C H ₂ ), 3.84 (t, 8H, Ar-OC H ₂
-R), 3.14 (d, 4H, Ar-C H ₂ ), 1.91 (hextet, 8H, Ar-O-CH
₂ -C H ₂ -CH ₃ ), 0.98 (t, 12H, Ar-O-CH ₂ -CH ₂ -C H ₃ ).

(4) Synthesis of tetra-p-iodinated tetrapropoxycalix [4] arene After drying 0.7 g of the compound synthesized in the above (3),
Immediately after the distillation, it was melted in 100 ml of chloroform and further stirred under a nitrogen stream while stirring silver trifluoroacetate 1.
35 g was added. This was refluxed for 20 minutes, 1.58 g of iodine was added, and the reflux was continued for another 1 hour. The reaction mixture was hot filtered, the filtrate was allowed to cool and then washed with a saturated aqueous solution of sodium metabisulfite. The organic layer was washed with water and dried, and then the solvent was distilled off. After purifying the target product by passing it through a silica gel column with a mixed solution of hexane and methylene chloride, the product was finally recrystallized from a mixed solvent of chloroform and methanol to obtain 0.97 g.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 6.99 (s, 8
H, Ar H ), 4.29 (d, 4H, Ar-C H ₂ ), 3.80 (t, 8H, Ar-OC H ₂
-R), 3.05 (d, 4H, Ar-C H ₂ ), 1.85 (hextet, 8H, Ar-O-CH
₂ -C H ₂ -CH ₃ ), 0.95 (t, 12H, Ar-O-CH ₂ -CH ₂ -C H ₃ ).

(5) Synthesis of p-hexadecyloxybenzaldehyde 5.2 g of 1-hexadecane bromide, 2 g of p-hydroxybenzaldehyde and 5.8 g of potassium carbonate were added to acetone 1
It was thawed to 00 ml and heated to reflux overnight. The obtained solid was filtered off, washed with warm acetone and added to the filtrate, and then the solvent acetone was distilled off. The residue was purified by flowing through a silica gel column with methylene chloride to obtain 3 g of the desired product.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 9.89 (s, 1
H, Ar-C H O), 7.82 (d, 2H, Ar H ), 6.98 (d, 2H, Ar H ), 4.
04 (t, 2H, -OC H ₂ ), 1.81 (m, 2H, -OCH ₂ C H ₂ ), 1.5 ~ 1.3
(m, 26H, -C H _2- ), 0.88 (t, 3H, -C H ₃ ).

(6) Synthesis of p-hexadecyloxybenzylacetylene After dissolving 2 g of potassium butoxide in 75 ml of tetrahydrofuran immediately after distillation, 3 g of triphenylphosphinium bromide bromide was added at -78 ° C. After stirring this for 5 minutes, a solution prepared by dissolving 2.4 g of the aldehyde synthesized in the above (5) in 50 ml of tetrahydrofuran was added dropwise to the solution. The reaction mixture was allowed to stand at room temperature and stirred overnight under a nitrogen stream. 30 ml of water was added thereto, the organic phase was extracted with hexane, and then dried over anhydrous magnesium sulfate. After evaporating the solvent, the obtained solid was purified by a silica gel column using a mixed solvent of hexane and methylene chloride to obtain 1.5 g of the desired product.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 9.89 (s, 1
H, Ar-C H O), 7.41 (d, 2H, Ar H ), 6.82 (d, 2H, Ar H ), 3.
94 (t, 2H, -OC H ₂ ), 2.98 (s, 1H, C≡C− H ), 1.77 (m, 2H,
-OCH ₂ C H ₂ ), 1.5 to 1.3 (m, 26H, -C H _2- ), 0.88 (t, 3H,-
C H ₃ ).

(7) Synthesis of tetra-p- (p-hexadecyloxybenzylacetylene) tetra-p-propoxycalix [4] arene 0.52 g of benzylacetylene synthesized in the above (6) and (4) were synthesized. 0.2 g of calixarene was dissolved in 40 ml of tripropylamine and suctioned to remove the gas. Tetratriphenylphosphine palladium and copper iodide were added in catalytic amounts, and the mixture was stirred at 50 ° C. for 2 hours and a half. After cooling with an ice bath to terminate the reaction, 200 ml of concentrated hydrochloric acid was added. The solution was extracted with ethyl acetate, the obtained organic phase was dried over magnesium sulfate, and then the solvent was distilled off. The obtained solid was purified with a silica gel column using a mixed solvent of methylene chloride and hexane. The isolated solid was recrystallized from acetone again to obtain 0.28 g of the desired product.

The results of ¹ H NMR (CDCl ₃ ) analysis of the obtained substance are as follows. ¹ H NMR (CDCl ₃ ) σ (ppm): 7.32 (d, 8
H, J = 8.5, Ar H ) 6.92 (s, 8H, Ar H ), 6.67 (d, 8H, J =
8.5, Ar H ), 4.29 (d, 4H, J = 13.5, Ar-C H ₂ ), 3.89 (t,
16H, J = 7, Ar-OC H ₂ -R), 3.15 (d, 4H, J = 13.5, Ar-
C H ₂ ), 1.92 (hextet, 8H, J = 7.7, Ar-O-CH ₂ -C H ₂ -CH ₃ ),
1.75 (hextet, 8H, J = 7.7, Ar-O-CH ₂ -C H ₂ -R), 1.25
(m, 92H, CH ₂ (C H ₂ ) ₁₃ CH ₃ ), 0.99 (t, 12H, J = 7, Ar-O-
CH ₂ -CH ₂ -C H ₃ ), 0.87 (t, 12H, J = 7.5, RC H ₃ ).

As a result of elemental analysis of the substance obtained here, measured value (%) [theoretical value (%)]: C 83.45
[83.54] and H 10.10 [9.92] were obtained. From these values, it was found that the molecular structure of the obtained compound was in agreement with the target compound, tetra-p- (p-hexadecyloxybenzylacetylene) tetra-p-propoxycalix [4] arene, Synthesis was confirmed.

Example 2 Synthesis of dodecyloxy derivative (C12) Synthesis of tetra-p- (p-dodecyloxybenzylacetylene) tetra-p-propoxycalix [4] arene (5) and (6) of Example 1 In the same manner, using a dodecyloxy derivative instead of the hexadecyloxy derivative,
A benzylacetylene derivative was synthesized. The obtained benzylacetylene derivative was reacted with the calixarene synthesized in (4) above in the same manner as in (7) above to obtain the desired compound.

Example 3 Investigation of liquid crystallinity The compounds C ₁₂ H ₂₅ obtained in Example 1 and Example 2 were obtained by DSC measurement, X-ray diffraction measurement and liquid crystal texture observation by a polarization microscope equipped with a temperature controller. The liquid crystallinity of the compound C ₁₆ H ₃₃ was examined.

Table 1 shows the thermotropic liquid crystallinity (phase transition temperature and emerging liquid crystal phase) of each compound.

[0040]

[Table 1]

Table 2 shows the lyotropic liquid crystallinity (solvent and emerging liquid crystal phase) of each compound.

[0042]

[Table 2]

From the above, it was found that the two kinds of compounds synthesized by changing the alkyl chain length according to the present invention have similar liquid crystallinity.

[0044]

Since the liquid crystal phase of the compound of the present invention has a column structure formed by stacking cone-shaped molecules, it is deeply involved in a form of expressing one function of optoelectronic properties such as a function of switching electrical characteristics, It can be applied to new liquid crystal materials in the future.

The characteristic feature of the liquid crystal compound of the present invention is that it has antiparallel column alignment. By utilizing this characteristic and the self-organizing property of liquid crystallinity, it is possible to construct a migration path of charge carriers such as electrons, holes, and ions in a molecular size (nano size).

Therefore, the compound of the present invention can be utilized as various electronic materials having a nanostructure having an electronic / optical function such as photo-electron conversion, electrophotographic photoreceptor characteristics, charge transportability, and device technology.

Since the lyotropic liquid crystal phase generally has a lower viscosity than the thermotropic liquid crystal phase, the compound of the present invention can easily control the molecular orientation by a weak external field such as an electric field. Therefore, when it is necessary to prepare a thin film by using the compound of the present invention having both the thermotropic liquid crystallinity and the lyotropic liquid crystallinity and further to align the molecules (or columns) in one direction in the film. In addition, it is possible to fabricate the alignment film under advantageous conditions.

[Brief description of drawings]

FIG. 1 shows a liquid crystal compound of the present invention.

FIG. 2 shows a stacked column structure of the cone-shaped molecule shown in FIG. 1 and its arrangement.

Continued front page    (72) Inventor Jarvis Helen             1-83-1 Midorigaoka, Ikeda, Osaka Prefecture             AIST Kansai Center F-term (reference) 4H006 AA01 AB64 GP03

Claims (4)

[Claims] 1. A chemical formula (1); _{(Wherein, R = C n H 2n +} 1; n is an integer of 5-23) liquid crystal compound characterized by having a chemical structure represented by. 2. The liquid crystalline compound according to claim 1, which has a thermotropic liquid crystalline property and a lyotropic liquid crystalline property. 3. The liquid crystal compound according to claim 1, having a liquid crystal phase having a column structure. 4. The liquid crystal compound according to claim 1, wherein R is an alkyl chain having 5 to 23 carbon atoms.