WO2012108484A1

WO2012108484A1 - Liquid crystalline styryl derivative, method for producing same, electrically conductive liquid crystal material, and organic semiconductor device.

Info

Publication number: WO2012108484A1
Application number: PCT/JP2012/052913
Authority: WO
Inventors: 原本　雄一郎
Original assignee: 日本化学工業株式会社; 国立大学法人山梨大学
Priority date: 2011-02-10
Filing date: 2012-02-09
Publication date: 2012-08-16
Also published as: JPWO2012108484A1; JP5980693B2

Abstract

The present invention provides a liquid crystalline styryl derivative which has excellent electrical conductivity, in which molecular orientation is controlled by a rubbing treatment and in which liquid crystal molecules are oriented in a direction parallel to a substrate, a method for producing the liquid crystalline styryl derivative, an electrically conductive liquid crystal material containing the liquid crystalline styryl derivative, and an organic semiconductor device. A liquid crystalline styryl derivative is characterized in being represented by general formula (1). The liquid crystalline styryl derivative is such that n is preferably 1 in general formula (1). [Formula 1] (In the formula, R¹ denotes an alkyl group and n is an integer between 1 and 3.)

Description

Liquid crystalline styryl derivative, method for producing the same, conductive liquid crystal material, and organic semiconductor element

The present invention relates to a liquid crystalline styryl derivative having excellent conductivity useful as an organic semiconductor and capable of controlling the alignment of liquid crystal molecules by rubbing treatment, a production method thereof, a conductive liquid crystal material, and an organic semiconductor element. .

In recent years, research on organic electroluminescent elements using organic materials as hole transport materials and conductive liquid crystal materials constituting the electroluminescent elements has been actively conducted.

As such conductive liquid crystal materials, conventionally, anthracene derivatives, anthraquinoline derivatives, imidazole derivatives, oligothiophene derivatives, styryl derivatives, hydrazone derivatives, triphenylamine compounds, poly-N-vinylcarbazole, oxadiazole, etc. Are known. Hanna et al. Have proposed a liquid crystal compound having a smectic A phase as a liquid crystal phase and having a charge transporting ability, and a conductive liquid crystal material using these compounds (see, for example, Patent Documents 1 to 3).

However, excellent charge transport ability is not expressed unless excited by light or the like, and the value is as low as nano A / cm ² even if the current density is large. Further, those having a carbonyl group in the structure or oligothiophene derivatives decomposed at a temperature of about 300 ° C. and had a problem in durability at high temperatures.

The present inventor previously applied a charge transport method in which a voltage is applied to a liquid crystalline compound having a smectic B phase as a liquid crystal phase in a liquid crystal state of the smectic B phase or a solid state generated by the phase transition of the smectic B phase (see Patent Document 4). ), A charge transport method using liquid crystal molecules having a long linear conjugated structure (see Patent Document 5) has been proposed.

The liquid crystal compound that the present inventors are paying attention to is a rod-like compound having chain-like alkyl hydrocarbon branch portions on both sides (or one side) of a long linear conjugated structure portion (hereinafter referred to as “core portion”). It is. This liquid crystal compound is durable even at a high temperature of 300 ° C., and has a feature that the core portion is easily aligned so as to be stacked in parallel by the interaction of the chain hydrocarbon portion. The core portion forms a conjugated system by an aromatic ring or multiple bonds so that π electrons can move. Therefore, since the charge transport property is remarkably increased by aligning the core portions in parallel, in order to use this compound as an organic semiconductor element, the control of the alignment is extremely important.

As a conventional method of forming a thin film by controlling molecular orientation with conductive liquid crystal molecules, a vapor deposition film is formed by oblique vapor deposition by the PVD method, and the vapor deposition film is then heat-treated in the temperature range of the smectic phase of the liquid crystal compound. (For example, refer to Patent Document 6).

JP 09-316442 A Japanese Patent Laid-Open No. 11-162648 JP-A-11-199871 JP 2001-351786 A JP 2004-6271 A JP 2005-142233 A

The method of forming a thin film by oblique deposition has a problem that the manufacturing cost increases because the deposition apparatus is expensive and the productivity is low.

As a method for controlling the alignment of a liquid crystal material, a method is known in which the surface of an alignment film made of a polymer material such as polyimide is rubbed in a certain direction and liquid crystal molecules are aligned along the rubbing direction. This rubbing treatment can be said to be the most industrially advantageous method because the molecular orientation of the liquid crystal molecules can be controlled by a simple operation.

Conventional conductive liquid crystal compounds have a problem that it is difficult to control molecular orientation by rubbing treatment.

Accordingly, the present invention provides a liquid crystalline styryl derivative having excellent conductivity and capable of controlling molecular orientation by rubbing treatment, a method for producing the same, a conductive liquid crystal material using the liquid crystalline styryl derivative, and an organic An object is to provide a semiconductor device.

As a result of intensive studies in view of the above circumstances, the present inventors have found that a novel liquid crystalline styryl derivative represented by a specific general formula has excellent conductivity and is effective against organic solvents such as hexane. In addition, the present inventors found that the liquid crystalline styryl derivative can easily control the molecular orientation by rubbing treatment and can orient the liquid crystal molecules in parallel to the substrate. It came to completion.

That is, the first invention to be provided by the present invention is a liquid crystalline styryl derivative represented by the following general formula (1).

(Wherein R ¹ represents an alkyl group, and n represents an integer of 1 to 3)

The second invention to be provided by the present invention is the following general formula (2a).

An aldehyde compound represented by the following general formula (3a)

(Wherein R ¹ has the same meaning as described above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1A) of the first invention:

(Wherein R ¹ is as defined above), a method for producing a liquid crystalline styryl derivative.

The third invention to be provided by the present invention is the following general formula (2b).

(Wherein R ¹ is as defined above), and the following general formula (3b)

(Wherein R ¹ is as defined above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1B) of the first invention,

The fourth invention to be provided by the present invention is the following general formula (2b).

(Wherein R ¹ is as defined above) and the following general formula (3c)

The following general formula (1C) of the first invention, characterized by reacting with a phosphorus compound represented by the formula:

The fifth invention to be provided by the present invention is the following general formula (2a).

An aldehyde compound represented by the following general formula (3b)

(Wherein R ¹ has the same meaning as described above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1C) of the first invention:

Further, a sixth invention to be provided by the present invention is the following general formula (2b)

(Wherein R ¹ is as defined above) and the following general formula (a4)

(Wherein R ¹ has the same meaning as described above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1C)

(Wherein, R ¹ is as defined above). The method for producing a liquid crystalline styryl derivative according to claim 1.

Also, a seventh invention to be provided by the present invention is a conductive liquid crystal material characterized by containing the liquid crystalline styryl derivative of the first invention.

Also, an eighth invention to be provided by the present invention is an organic semiconductor element characterized by using the conductive liquid crystal material of the seventh invention.

The liquid crystalline styryl derivative provided by the present invention is a novel compound and has excellent conductivity. In addition, since it exhibits excellent solubility in an organic solvent such as hexane, a printing method can be applied as a film forming method of the liquid crystal styryl derivative of the present invention. Further, the liquid crystalline styryl derivative of the present invention is rubbed. Thus, the molecular orientation can be easily controlled, and the liquid crystal molecules can be oriented parallel to the substrate.

It is the schematic which shows one Embodiment of the organic-semiconductor element of this invention. The schematic diagram which shows the cross-section of one organic electroluminescent element of embodiment using the organic-semiconductor element of this invention. The schematic diagram which shows the cross-section of one organic electroluminescent element of embodiment using the organic-semiconductor element of this invention. The schematic diagram which shows the cross-section of one thin-film transistor element of embodiment using the organic-semiconductor element of this invention. The schematic diagram which shows the cross-section of an organic electroluminescent element provided with one thin-film transistor element of embodiment using the organic-semiconductor element of this invention. A polarizing microscope photograph in a solid state after sandwiching the styryl derivative obtained in Example 1 and Reference Example 1 between glass substrates subjected to rubbing treatment, and then heating to an isotropic liquid temperature or higher and then cooling to room temperature. 3 is a graph showing the relationship between the temperature of an element using a conductive liquid crystal material containing a styryl derivative obtained in Example 1 and the amount of current. FIG. 3 is a graph showing the relationship between the voltage and current density of an element using a solid obtained by heat-treating and cooling the conductive liquid crystal material containing the styryl derivative obtained in Example 1 into an isotropic liquid state. The figure which shows the relationship between the temperature of an element using the electroconductive liquid crystal material obtained by the reference example 2, and electric current amount.

The liquid crystalline styryl derivative according to the first aspect of the present invention is a liquid crystalline compound having a long linear conjugated structure portion, and the liquid crystalline styryl derivative has a smectic phase in a liquid crystal state. The liquid crystalline styryl derivative of the present invention is characterized by having three substituents on the benzene rings of the styryl groups at both ends in the general formula (1). Due to this feature, the liquid crystalline styryl derivative of the present invention is further excellent in electrical conductivity, and the molecular alignment can be easily controlled by rubbing treatment to align the liquid crystal molecules in parallel with the substrate.

In general formula (1), R ¹ is a linear or branched alkyl group, and an alkyl group having 1 to 18 carbon atoms is preferably used. Specific examples include a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a pentadecyl group, and an octadecyl group. Of these, an alkyl group having 4 to 18 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable. In addition, the alkyl group has the general formula CH ₃ — (CH ₂ ) x—CH (CH ₃ ) — (CH ₂ ) y—CH ₂ — (wherein x is an integer from 0 to 7 and y is an integer from 0 to 7) The solubility in various solvents can be improved.
In the general formula (1), n represents an integer of 1 to 3, preferably 1.

The liquid crystalline styryl derivative represented by the general formula (1) may be a cis isomer or a trans isomer, or a mixture of both.

Hereinafter, the manufacturing method of the styryl derivative represented by General formula (1) of this invention is demonstrated.
The styryl derivative represented by the general formula (1A) according to the second invention of the present invention is suitable by reacting the aldehyde compound represented by the general formula (2a) with the phosphorus compound represented by the general formula (3a). Can be manufactured.

As the aldehyde compound represented by the general formula (2a) of the raw material according to the second invention, a commercially available product can be used.

R ¹ in the formula of the phosphorus compound represented by the general formula of the material of the second aspect of the invention (3a) is a corresponding group R ¹ in the general formula (1A).
The phosphorus compound represented by the general formula (3a) can be produced, for example, according to the following reaction scheme (1).

(In the formula, R ¹ and Et are as defined above.)

In Reaction Scheme 1, first, gallic acid (4) is reacted in a solvent such as alkyl bromide (5) and dimethylformamide in the presence of a base such as potassium carbonate, preferably at 40 to 80 ° C. for 5 hours or more. Compound (6) is obtained. Next, the compound (6) obtained is reacted with a base such as lithium aluminum halide in a solvent such as ether, preferably at 30 to 50 ° C. for 2 hours or longer to obtain the compound (7). Next, the obtained compound (7) and phosphorus tribromide are reacted in a solvent such as toluene in the presence of a base such as pyridine, preferably at 20 to 50 ° C. for 20 hours or longer to obtain compound (8). . Next, the obtained compound (8) and triethyl phosphite can be reacted in a nitrogen atmosphere, preferably at 100 to 150 ° C. for 5 hours or longer to obtain the phosphorus compound (3a).

In the method for producing a liquid crystalline styryl derivative represented by the general formula (1A) according to the second invention, the addition amount of the phosphorus compound of the general formula (3a) is a molar ratio with respect to the aldehyde compound represented by the general formula (2a). It is 1.8 to 2.5, preferably 1.9 to 2.1.

In the second invention, the reaction of the aldehyde compound represented by the general formula (2a) and the phosphorus compound of the general formula (3a) is performed in a solvent in the presence of a base.

Examples of the base that can be used in the second invention include metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide and potassium methoxide. Alkoxide such as sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, pyridine, potassium cresolate, alkyllithium and the like, and these may be used alone or in combination. The amount of the base added is 2.0 to 5.0, preferably 3.0 to 4.0, as a molar ratio to the aldehyde compound represented by the general formula (2a).

The reaction solvent that can be used in the second invention is not particularly limited as long as it can dissolve the raw materials and is inert to the product. For example, ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water can be used alone or in combination. .

The reaction conditions according to the second invention are a reaction temperature of 10 to 100 ° C., preferably 40 to 70 ° C., and a reaction time of 5 hours or more, preferably 15 to 50 hours.

In the second aspect of the invention, the reaction is stopped by adding an acid such as hydrochloric acid to the reaction solution. After the reaction is completed, the reaction solvent is removed by distillation or the like, washing is performed as necessary, and recrystallization or column chromatography is performed as necessary. The target liquid crystalline styryl derivative represented by the general formula (1A) can be obtained by purification by a conventional method such as chromatography.

The styryl derivative represented by the general formula (1B) according to the third invention of the present invention is suitable by reacting the aldehyde compound represented by the general formula (2b) and the phosphorus compound represented by the general formula (3b). Can be manufactured.

R ^{1 in} the formula of the aldehyde compound represented by the general formula (2b) of the third invention is a group corresponding to R ^{1 in} the formula of the liquid crystalline styryl derivative represented by the general formula (1B).
The aldehyde compound represented by the general formula (2b) of the third invention can be produced, for example, according to the following reaction scheme (2).
In the following reaction scheme (2), first, gallic acid (4) is reacted with alkyl bromide (5) in the presence of a base such as potassium carbonate to obtain compound (6). Next, compound (7) is obtained by reacting the obtained compound (6) with a base such as lithium aluminum halide. Next, the compound (7) obtained is reacted with phosphorus tribromide to obtain the compound (8). Next, the compound (8) and triphenylphosphine obtained are reacted to obtain the compound (a2). Next, by reacting the obtained compound (a2) with terephthalaldehyde (2a), the desired aldehyde compound represented by the general formula (2b) can be obtained (for example, JP-A-2007-217309). See the official gazette).

Further, the aldehyde compound represented by the general formula (2b) is obtained by combining the phosphorus compound represented by the general formula (3a) and terephthalaldehyde (aldehyde compound (2a)) with a phosphorus compound (3a) for terephthalaldehyde (2a). ) In a molar ratio of 0.5 to 0.8 and in the presence of a base such as potassium t-butoxide in a solvent such as tetrahydrofuran at 10 to 60 ° C. for 3 hours or longer.

In addition, when the obtained aldehyde compound represented by the general formula (2b) is a mixture of a cis isomer and a trans isomer, if necessary, the aldehyde compound is reacted with iodine while refluxing the mixture in toluene. The trans form of is obtained. In this case, the amount of iodine added is preferably 0.001 to 0.1 times mol, more preferably 0.005 to 0.01 times mol, with respect to the aldehyde compound represented by the general formula (2b). The treatment temperature is 100 to 180 ° C, preferably 130 to 150 ° C.

R ^{1 in} the formula of the phosphorus compound represented by the general formula (3b) is a group corresponding to R ^{1 in} the formula of the styryl derivative represented by the general formula (1B).
The phosphorus compound represented by the general formula (3b) can be produced, for example, according to the following reaction scheme (3).
In the following reaction scheme (3), first, 3,4,5-trihydrobenzaldehyde (a1) is reacted with alkyl bromide (5) to obtain compound (a3) (for example, JP-A-2007-137809). See the official gazette). Next, the target phosphorus compound represented by the general formula (3b) can be obtained by reacting the obtained compound (a3) with tetraethyl p-xylylene diphosphonate (phosphorus compound (a4)) ( For example, JP 2009-250817 A).

(Wherein R ¹ has the same meaning as described above.)

In the method for producing a liquid crystalline styryl derivative represented by the general formula (1B) according to the third invention, the addition amount of the phosphorus compound of the general formula (3b) is a molar ratio with respect to the aldehyde compound represented by the general formula (2b). It is 0.9 to 1.1, preferably 0.95 to 1.05.

The reaction of the third invention of the present invention is performed by reacting the aldehyde compound represented by the general formula (2b) and the phosphorus compound represented by the general formula (3b) in a solvent in the presence of a base.

Examples of the base that can be used in the third invention include metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide and potassium methoxide. Alkoxide such as sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, pyridine, potassium cresolate, alkyllithium and the like, and these may be used alone or in combination. The amount of the base added is 2.0 to 5.0, preferably 2.0 to 4.0, as a molar ratio to the aldehyde compound represented by the general formula (2b).

The reaction solvent that can be used in the third invention is not particularly limited as long as it can dissolve the raw material and is inert to the product. For example, ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water can be used alone or in combination. .

The reaction conditions according to the third invention are a reaction temperature of 10 to 100 ° C., preferably 10 to 40 ° C., and a reaction time of 5 hours or more, preferably 10 to 30 hours.

In the third aspect of the invention, the reaction is stopped by adding an acid such as hydrochloric acid to the reaction solution, and after completion of the reaction, the reaction solvent is removed by distillation or the like, washing is performed if necessary, and recrystallization or column chromatography is performed if necessary. The target liquid crystalline styryl derivative represented by the general formula (1B) can be obtained by purification by a conventional method such as chromatography.

The styryl derivative represented by the general formula (1C) can be preferably produced by the fourth and fifth inventions described later.

According to a fourth aspect of the present invention, a styryl derivative represented by the general formula (1C) is obtained by reacting an aldehyde compound represented by the general formula (2b) with a phosphorus compound represented by the general formula (3c). It is.

R ^{1 in} the formula of the aldehyde compound represented by the general formula (2b) according to the fourth invention is a group corresponding to R ¹ in the formula of the liquid crystalline styryl derivative represented by the general formula (1C), As the aldehyde compound represented by the general formula (2b), the aldehyde compound represented by the same general formula (2b) as in the third invention can be used.

As the phosphorus compound represented by the general formula (3c) of one raw material according to the fourth invention, a commercially available product can be used.

In the method for producing a liquid crystalline styryl derivative represented by the general formula (1C) according to the fourth invention, the addition amount of the phosphorus compound of the general formula (3c) is a molar ratio with respect to the aldehyde compound represented by the general formula (2b). It is 0.9 to 1.1, preferably 0.95 to 1.05.

The reaction of the fourth invention of the present invention is carried out by reacting the aldehyde compound represented by the general formula (2b) and the phosphorus compound represented by the general formula (3c) in a solvent in the presence of a base.

Examples of the base that can be used in the fourth invention include metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide and potassium methoxide. Alkoxide such as sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, pyridine, potassium cresolate, alkyllithium and the like, and these may be used alone or in combination. The amount of the base added is 2.0 to 5.0, preferably 2.0 to 4.0, as a molar ratio to the aldehyde compound represented by the general formula (2b).

The reaction solvent that can be used in the fourth invention is not particularly limited as long as it can dissolve the raw materials and is inert to the product. For example, ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water can be used alone or in combination. .

The reaction conditions according to the fourth invention are a reaction temperature of 10 to 100 ° C., preferably 10 to 40 ° C., and a reaction time of 5 hours or more, preferably 10 to 50 hours.

In the fourth aspect of the invention, the reaction is stopped by adding an acid such as hydrochloric acid to the reaction solution, and after completion of the reaction, the reaction solvent is removed by distillation or the like, washing is performed if necessary, and recrystallization or column chromatography is performed if necessary. The target liquid crystalline styryl derivative represented by the general formula (1C) can be obtained by purification by a conventional method such as chromatography.

According to a fifth aspect of the present invention, a styryl derivative represented by the general formula (1C) is obtained by reacting an aldehyde compound represented by the general formula (2a) with a phosphorus compound represented by the general formula (3b). It is.

As the aldehyde compound represented by the general formula (2a) according to the fifth invention, the aldehyde compound represented by the same general formula (2a) as that of the second invention can be used.
On the other hand, R ^{1 in} the formula of the phosphorus compound represented by (3b) according to the fifth invention is a group corresponding to R ¹ in the formula of the general formula (1C). The phosphorus compound represented by the same general formula (3b) as the invention can be used.

In the method for producing a liquid crystalline styryl derivative represented by the general formula (1C) according to the fifth invention, the addition amount of the phosphorus compound of the general formula (3b) is a molar ratio with respect to the aldehyde compound represented by the general formula (2a). It is 0.4 to 0.7, preferably 0.45 to 0.6.

The reaction of the fifth invention of the present invention is carried out by reacting an aldehyde compound represented by the general formula (2a) and a phosphorus compound represented by the general formula (3b) in a solvent in the presence of a base.

Examples of the base that can be used in the fifth invention include metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide and potassium methoxide. Alkoxide such as sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, pyridine, potassium cresolate, alkyllithium and the like, and these may be used alone or in combination. The amount of the base added is 2.0 to 5.0, preferably 2.0 to 4.0, as a molar ratio to the aldehyde compound represented by the general formula (2a).

The reaction solvent that can be used in the fifth invention is not particularly limited as long as it can dissolve the raw materials and is inert to the product. For example, ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water can be used alone or in combination. .

The reaction conditions according to the fifth invention are such that the reaction temperature is 10 to 100 ° C., preferably 10 to 40 ° C., and the reaction time is 5 hours or more, preferably 10 to 50 hours.

In the fifth invention, the reaction is stopped by adding an acid such as hydrochloric acid to the reaction solution, and after the reaction is completed, the reaction solvent is removed by distillation or the like, washing is performed if necessary, and recrystallization or column chromatography is performed if necessary. The target liquid crystalline styryl derivative represented by the general formula (1C) can be obtained by purification by a conventional method such as chromatography.

According to a sixth aspect of the present invention, there is provided a styryl derivative represented by the general formula (1C) by reacting an aldehyde compound represented by the general formula (2b) with a phosphorus compound represented by the general formula (a4). To get.

As the aldehyde compound represented by the general formula (2b) according to the sixth invention, the aldehyde compound represented by the same general formula (2b) as in the third invention can be used. R ^{1 in} the formula of the aldehyde compound represented by 2b) is a group corresponding to R ¹ in the formula of the liquid crystalline styryl derivative represented by the general formula (1C).

On the other hand, the phosphorus compound represented by (a4) according to the sixth invention can be easily produced by reacting α, α'-dichloro-p-xylene and triethyl phosphite.

In the method for producing a liquid crystalline styryl derivative represented by the general formula (1C) according to the sixth invention, the addition amount of the phosphorus compound of the general formula (a4) is a molar ratio with respect to the aldehyde compound represented by the general formula (2b). It is 0.4 to 0.7, preferably 0.45 to 0.6.

The reaction of the sixth invention of the present invention is carried out by reacting the aldehyde compound represented by the general formula (2b) and the phosphorus compound represented by the general formula (a4) in a solvent in the presence of a base.

Examples of the base that can be used in the sixth invention include metal hydrides such as sodium hydride, amines such as trimethylamine and triethylamine, alkali hydroxides such as potassium hydroxide and sodium hydroxide, sodium methoxide and potassium methoxide. Alkoxide such as sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, pyridine, potassium cresolate, alkyllithium and the like, and these may be used alone or in combination. The addition amount of the base is 2.0 to 6.0, preferably 4.0 to 6.0 in terms of a molar ratio to the aldehyde compound represented by the general formula (2b).

The reaction solvent that can be used in the sixth invention is not particularly limited as long as it can dissolve the raw material and is inert to the product. For example, ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water can be used alone or in combination. .

The reaction conditions according to the sixth invention are such that the reaction temperature is 10 to 100 ° C., preferably 10 to 40 ° C., and the reaction time is 5 hours or more, preferably 10 to 50 hours.

In the sixth aspect of the invention, the reaction is stopped by adding an acid such as hydrochloric acid to the reaction solution, and after completion of the reaction, the reaction solvent is removed by distillation or the like, washing is performed if necessary, and recrystallization or column chromatography is performed if necessary. The target liquid crystalline styryl derivative represented by the general formula (1C) can be obtained by purification by a conventional method such as chromatography.

The various liquid crystalline styryl derivatives represented by the general formula (1) ((1A), (1B), (1C)) obtained by the second to sixth inventions are more conductive than the conventional liquid crystalline styryl derivatives. Excellent solubility in organic solvents such as hexane. In addition, the liquid crystalline styryl derivative can easily control the molecular alignment by rubbing treatment, and can align the liquid crystal molecules in parallel with the substrate.

Next, the conductive liquid crystal material according to the seventh aspect of the present invention will be described.
The conductive liquid crystal material of the present invention contains 50% by weight or more, preferably 80% by weight or more of the liquid crystalline styryl derivative represented by the general formula (1), and exhibits a liquid crystal state of a smectic phase caused by the liquid crystalline styryl derivative. It is a material to show.

When the liquid crystalline styryl derivative represented by the general formula (1) is used in a mixture of two or more, the temperature range showing the liquid crystal can be widely adjusted.

Further, as other components to be included in the conductive liquid crystal material, for example, conductive organic liquid crystal compounds such as a liquid crystal compound having a long linear conjugated structure portion (see, for example, JP-A-2004-6271) and the like. Is raised.

The conductive liquid crystal material of the present invention is composed of two or more kinds of liquid crystalline styryl derivatives represented by the general formula (1), or a composition with other components such as a liquid crystalline styryl derivative represented by the general formula (1). After dissolving one or more kinds and other necessary components in a solvent, the solvent is removed by heating, reduced pressure, or the like, or one or more kinds of styryl derivatives represented by the general formula (1) and the same It can be prepared by mixing with other necessary components and melting by heating, or performing sputtering, vacuum deposition, oblique vacuum deposition or the like.

The conductive liquid crystal material of the present invention is preferably used as a thin film. As a method for forming the thin film, vacuum deposition or oblique vacuum deposition can be used, but one or more desired components of the styryl derivative represented by the general formula (1) and other necessary requirements These components can be dissolved in a solvent and formed into a layer by dip coating, spin coating, screen printing, or ink jet printing, which makes it easy to create an organic thin film, which is also industrially advantageous. is there.

The conductive liquid crystal material of the present invention preferably exhibits charge transporting ability by the following two methods.
(A) A method of applying a voltage to the conductive liquid crystal material in a liquid crystal state of a smectic phase.
(B) A method of applying a voltage to the conductive liquid crystal material in a solid state generated by a phase transition from a smectic phase.

The method (a) is a method in which the conductive liquid crystal material is made into a smectic phase at a predetermined temperature, and a voltage is applied in the liquid crystal state of the smectic phase to transport charges. In this case, the smectic phase may be in any state of A, B, C, D, E, F, G, and H.

In the method (b), the conductive liquid crystal material is changed to a smectic phase at a predetermined temperature, and the temperature is lowered from this state to obtain a solid state that maintains the molecular orientation of the smectic phase. In this method, a voltage is applied to the electrode to transport charges. As a method for lowering the temperature, natural cooling may be used, or rapid cooling may be used.

Next, an organic semiconductor element according to an eighth aspect of the present invention is characterized by using the conductive liquid crystal material.

The organic semiconductor element of the present invention is characterized in that a conductive liquid crystal layer made of the conductive liquid crystal material is provided between a substrate provided with a pair of electrodes.

FIG. 1 is a schematic view showing an embodiment of an organic semiconductor element. In FIG. 1, the organic semiconductor element of the present invention is provided with electrodes 2a and 2b made of transparent electrodes such as ITO on the surfaces of two glass substrates 1a and 1b, respectively, and a pair of substrates provided with the electrodes is a spencer 4. A cell is formed by adhering with an adhesive while keeping the cell interval constant, and the conductive liquid crystal material is injected into the cell to provide the conductive liquid crystal layer 3 between the electrodes. The conductive liquid crystal layer 3 provided between the electrodes 2a and 2b is set to (a) a smectic phase liquid crystal state, and a voltage is applied in the smectic phase liquid crystal state, or the conductive liquid crystal layer 3 is set to (b ) By applying a voltage in the solid state generated by the phase transition from the smectic phase and applying a voltage in the solid state, a high current density can be obtained through the conductive liquid crystal layer 3, and charge can be transported.

Examples of the application of the organic semiconductor element according to the present invention include an organic electroluminescence element (EL element), a thin film transistor element, or an organic electroluminescence element including a thin film transistor element.

Hereinafter, application examples of the organic semiconductor element of the present invention will be described with reference to the drawings. 2 to 5 are schematic views showing one embodiment of the organic semiconductor element of the present invention. In the element of FIG. 2, an anode b2, a buffer layer b3, a conductive liquid crystal layer b4, and a cathode b5 are sequentially laminated on a transparent substrate b1. This element can be suitably used particularly as an organic electroluminescence element. As the substrate b1, a glass substrate usually used for an organic electroluminescence element is used. The anode b2 is made of a transparent material having a large work function for extracting light as necessary. For example, an ITO film is suitable. The cathode b5 is formed of a metal having a low work function, such as a thin film of Al, Ca, LiF, Mg, or an alloy thereof. As the conductive liquid crystal layer b4, the conductive liquid crystal material of the present invention is used, and the styryl derivative represented by the general formula (1) itself has blue to green luminescence, so the conductive liquid crystal layer b4 is a luminescent layer or a carrier transport layer. It has the function of. In this case, a smaller amount of a light emitting material can be added as long as the solid state generated by the phase transition from the smectic phase of the conductive liquid crystal material is maintained. Examples of luminescent materials that can be used include diphenylethylene derivatives, triphenylamine derivatives, diaminocarbazole derivatives, benzothiazole derivatives, benzoxazole derivatives, aromatic diamine derivatives, quinacridone compounds, perylene compounds, oxadiazole derivatives, coumarins. Examples thereof include laser compounds, anthraquinone derivatives, DCM-1 and other laser oscillation dyes, various metal complexes, low molecular fluorescent dyes, and polymeric fluorescent materials.
The conductive liquid crystal material of the present invention can also be suitably used as an organic layer in a portion in contact with the electrode.

In the emergency semiconductor element of the present invention, the conductive liquid crystal layer b4 is formed by subjecting the components of the conductive liquid crystal material to vacuum deposition or oblique vacuum deposition at the same time or separately at room temperature (5 to 40 ° C.). Each component of the conductive liquid crystal material may be prepared by subjecting each component of the conductive liquid crystal material to a solvent by applying a heat alignment treatment to the smectic liquid crystal state temperature range of the conductive liquid crystal material in an inert gas atmosphere such as argon or helium. After being dissolved in dip coating method, spin coating method, screen printing method, ink jet printing method, then the smectic liquid crystal state temperature range of the conductive liquid crystal material under an inert gas atmosphere such as nitrogen, argon, helium, etc. It is preferable from the viewpoint that a layer formed by adding a heat alignment treatment to can be produced at low cost.

The buffer layer b3 is provided as necessary, and is intended to lower the energy barrier for hole injection from the anode b2, and may use, for example, the conductive liquid crystal material of the present invention or other compounds. Good. Examples of other compounds include copper phthalocyanine, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate), other phenylamines, starburst amines, vanadium oxide, molybdenum oxide, oxidation Ruthenium, aluminum oxide, amorphous carbon, polyaniline, polythiophene derivatives and the like are used. Further, a buffer layer for the purpose of electron injection may be provided on the cathode b5 side.

3 is a schematic view showing an embodiment suitable for the case where the organic semiconductor element of the present invention is used as an organic electroluminescence element (EL element). In this element, an anode b2, a buffer layer b3, a conductive liquid crystal layer b4, an organic light emitting layer b6 and a cathode b5 are sequentially laminated on a transparent substrate b1, and the light emitting layer b6 is not a conductive liquid crystal layer. This is different from the embodiment of FIG. The light emitting layer b6 includes various conventional organic light emitting materials such as diphenylethylene derivatives, triphenylamine derivatives, diaminocarbazole derivatives, benzothiazole derivatives, benzoxazole derivatives, aromatic diamine derivatives, quinacridone compounds, perylene compounds, oxalates. Diazole derivatives, coumarin compounds, anthraquinone derivatives, laser oscillation dyes such as DCM-1, various metal complexes, low molecular fluorescent dyes, polymeric fluorescent materials, and the like are used.

In this embodiment, the conductive liquid crystal layer b4 uses the conductive liquid crystal material of the present invention, and the conductive liquid crystal layer b4 simultaneously or separately contains each component of the liquid crystal composition at room temperature (5 to 40 ° C.). After vacuum deposition or oblique vacuum deposition, it was created by applying a heat alignment treatment to the smectic liquid crystal state temperature range of the conductive liquid crystal material in an inert gas atmosphere such as nitrogen, argon, helium, etc. However, after dissolving each component of the conductive liquid crystal material in a solvent and applying it by the dip coating method, spin coating method, screen printing method, ink jet printing method, atmosphere of an inert gas such as nitrogen, argon, helium, etc. A layer formed by applying a heat alignment treatment to the smectic liquid crystal state temperature range of the conductive liquid crystal material below is preferable from the viewpoint that it can be produced at low cost.
In this case, the conductive liquid crystal layer b4 mainly functions as a carrier transport layer. However, the carrier transportability is higher than that of a conventional amorphous organic compound, so that the layer thickness can be increased and carrier injection efficiency can be increased. The effect of increasing the driving voltage and reducing the driving voltage can also be expected.

In the organic electroluminescence elements shown in FIGS. 2 and 3, the thickness of the conductive liquid crystal layer b4 can be arbitrarily designed in the range of 100 nm to 100 μm.

4 is a schematic view showing an embodiment suitable for the case where the liquid crystal semiconductor element of the present invention is used as a thin film transistor element. The thin film transistor (hereinafter referred to as “TFT”) is a field effect TFT in which a source b8 and a drain b9 are formed on a substrate b1 with a gate b7 interposed therebetween, and is insulated so as to cover the gate b7. A film b10 is formed, and a channel part b11 for energizing the source b8 and the drain b9 is provided outside the insulating film b10. For the substrate b1, an inorganic material such as glass or an alumina sintered body, an insulating material such as a polyimide film, a polyester film, a polyethylene film, a polyphenylene sulfide film, or a polyparaxylene film is used. The gate b7 is an organic material such as ponianiline or polythiophene, a metal such as gold, platinum, chromium, palladium, aluminum, indium, molybdenum or nickel, an alloy of these metals, polysilicon, amorphous silicon, tin oxide, indium oxide or indium. Tin oxide or the like is used. The insulating film b10 is preferably formed by applying an organic material. Examples of the organic material used include polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, cyanoethyl pullulan, poly Methyl methacrylate, polysulfone, polycarbonate, polyimide and the like are used. For the source b8 and the drain b9, gold, platinum, a transparent conductive film (indium / tin oxide, indium / zinc oxide, or the like) or the like is used. The channel portion b11 is made of the conductive liquid crystal material of the present invention, and the channel portion b11 allows the components of the conductive liquid crystal material to be simultaneously or separately vacuum-deposited or obliquely vacuum-deposited at room temperature (5 to 40 ° C.). Then, the material of the insulating film b10 may be prepared by applying a heat alignment treatment to the smectic liquid crystal state temperature range of the conductive liquid crystal material in an inert gas atmosphere such as nitrogen, argon, helium, etc. For example, after applying a rubbing treatment to polyimide using a polyimide, and applying the components of the conductive liquid crystal material dissolved in a solvent by a dip coating method, a spin coating method, a screen printing method, or an ink jet printing method Next, a heat alignment treatment is performed in the smectic liquid crystal state temperature range of the conductive liquid crystal material in an inert gas atmosphere such as nitrogen, argon, helium, etc. By forming a conductive liquid crystal layer on the outer layer of the insulating layer b10, it becomes possible to further improve the orientation of the conductive liquid crystal layer, thereby reducing the operating voltage of the TFT and increasing the operating speed. Can do. Moreover, p-type or n-type properties can be more emphasized by using in combination with an electron-accepting substance or an electron-donating substance if necessary. By applying an electric field from the gate b7 to the channel part b11 made of such a conductive liquid crystal material, the amount of holes or electrons inside the channel part b11 can be controlled to provide a function as a switching element. Further, it is desirable that the rubbing direction of the rubbing process is a direction perpendicular to the direction of the current flow path between the source b8 and the drain b9 (for example, the direction of the line connecting the centers of both). As a result, the side chain portion of the liquid crystalline styryl derivative having a long linear conjugated structure portion is aligned at right angles to the current flow path between the source and the drain, and the conjugated core portion is closely aligned, so that the carrier transport property is improved. It becomes extremely large, and shows conductivity at the semiconductor level such as silicon.

The element of FIG. 5 is a schematic view showing a cross-sectional structure of an organic electroluminescence element including one thin film transistor element of an embodiment using the organic semiconductor element of the present invention.
In this element, a TFT is formed as a switching element on the same substrate b1 as the electroluminescence element body, and the thin film transistor is used for this TFT. That is, adjacent to the electroluminescence element body, the source b8 and the drain b9 are formed on the substrate b1 so as to face each other across the gate b7. An insulating film b10 is formed so as to cover the gate b7, and a channel part b11 for conducting the source b8 and the drain b9 is formed outside the insulating film b10. The conductive liquid crystal material is used for the channel part b11. It is done. Since it is a matrix type pixel drive, the gate b7 and the source b8 are connected to the x and y signal lines, respectively, and the drain b9 is connected to one pole (in this example, the anode) of the electroluminescence element.

As the conductive liquid crystal material of the channel part b11, the same conductive liquid crystal material as that of the conductive liquid crystal layer b4 of the electroluminescence element body can be used, and it can be formed integrally therewith. As a result, in the active matrix type organic electroluminescence element, the element body and the TFT can be formed at the same time, and the manufacturing cost can be further reduced.

The conductive liquid crystal material of the channel portion b11 and the conductive liquid crystal layer b4 is obtained by subjecting the components of the liquid crystal composition to simultaneous or separate vacuum deposition or oblique vacuum deposition at room temperature (5 to 40 ° C.), and then nitrogen, argon The conductive liquid crystal material may be prepared by applying a heat alignment treatment to the smectic liquid crystal state temperature range in an inert gas atmosphere such as helium, but each component of the conductive liquid crystal material is used as a solvent. After dissolving and applying by dip coating method, spin coating method, screen printing method, ink jet printing method, then in the smectic liquid crystal state temperature range of the conductive liquid crystal material in an inert gas atmosphere such as nitrogen, argon, helium etc. A layer formed by applying a heat alignment treatment is preferable from the viewpoint that it can be produced at low cost.

The conductive liquid crystal material of the present invention can easily control the molecular alignment by rubbing treatment and align the liquid crystal molecules in parallel with the substrate. Since the conductive liquid crystal material of the present invention has this advantage, a thin film capacitor is preferable among the application examples of the organic semiconductor described above. In particular, the gate electrode, the source electrode and the drain electrode are formed so as to cover the gate electrode. And an insulating film formed on the outside of the insulating film, and a channel portion for connecting the source and drain electrodes formed on the outside of the insulating film. The channel portion is formed of a layer made of the conductive liquid crystal material of the present invention. Most preferably, polyimide is used for the channel portion of a thin film capacitor (see FIG. 4) which is configured to be rubbed to the insulating film to enhance the orientation of the conductive material of the outer layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
{Example 1}

Gallic acid (4) 0.058 mol (10 g) and potassium carbonate 0.116 mol (16 g) were dissolved in 50 ml of DMF. Then, it stirred at room temperature for 1 hour. Next, a solution prepared by dissolving 0.232 mol (58 g) of 1-bromododecane (5a) in 30 ml of DMF was added dropwise thereto. After dropping, the reaction was carried out by stirring overnight at 60 ° C. in a silicon bath.
After completion of the reaction, the reaction solution was extracted with 300 ml of cold dilute hydrochloric acid and 300 ml of diethyl ether, and then the extract was washed with water to remove DMF. Next, anhydrous sodium sulfate was added to the obtained ether layer and dehydrated overnight. Anhydrous sodium sulfate was removed by filtration, and diethyl ether was removed under reduced pressure by a rotary evaporator to obtain 30 g of Compound (6a) (yield 63%).

50 ml of diethyl ether was placed in a 500 ml three-necked flask, and 0.11 mol (4.0 g) of lithium aluminum hydride was added. A solution prepared by dissolving 0.036 mol (30 g) of compound (6a) in 50 ml of diethyl ether was slowly added dropwise thereto.
Next, the reaction was carried out in a silicon bath at 40 ° C. for 4 hours under reflux. After completion of the reaction, 7.5 g of ethyl acetate dissolved in 30 ml of diethyl ether was slowly added dropwise to the reaction solution under ice cooling. Next, 30 ml of a saturated aqueous ammonium chloride solution was slowly added dropwise, and the flask was filled with diethyl ether and stirred. Next, the mixture was centrifuged to obtain an ether layer. Diethyl ether was also added to the residue to obtain an ether layer, which was combined with the previously obtained ether layer. Next, the obtained ether layer was washed with 100 ml of 10% cold dilute hydrochloric acid and then dehydrated overnight with anhydrous sodium sulfate. After dehydration, diethyl ether was removed under reduced pressure using a rotary evaporator to obtain 20 g of Compound (7a) (yield 76%).

Into an Erlenmeyer flask, 15 g (0.023 mol) of the compound (7a) and 1.5 g of pyridine were added and dissolved in 50 ml of toluene.
In a 100 ml dropping funnel, 3 times moles of PBr ₃ of the compound (7a) was dissolved in 20 ml of toluene, and this was used as solution B.
The solution B was slowly added dropwise to the solution A prepared above over 30 minutes while cooling with ice. After dropping, the reaction was carried out at 40 ° C. for 2 days.
After completion of the reaction, the reaction solution was poured into 300 ml of ice water and extracted with 300 ml of diethyl ether. Next, it was washed several times with water, and anhydrous sodium sulfate was added to the obtained ether layer and dehydrated overnight. Next, filtration was performed to remove anhydrous sodium sulfate, and diethyl ether was removed under reduced pressure with a rotary evaporator to obtain 15 g of Compound (8a) (yield 88%).

Into an Erlenmeyer flask, 15 g (0.020 mol) of the compound (8a) and 3 times mole of the compound (8a) were added and triethyl phosphite was allowed to react at 130 ° C. for 17 hours in a nitrogen atmosphere.
After completion of the reaction, unreacted triethyl phosphite was removed under reduced pressure using a rotary evaporator to obtain 15 g of phosphorus compound (3a) (yield 90%).

In an Erlenmeyer flask, 15 g (0.020 mol) of the phosphorus compound (3a) and 1.4 g (0.010 mol) of terephthalaldehyde (2a) were added and dissolved in 50 ml of THF. 4.0 g (0.036 mol) of potassium tert-butoxide was added as a base and reacted at 50 ° C. for 2 days.
After completion of the reaction, 5 ml of 36% hydrochloric acid was added to stop the reaction, the mixture was concentrated with a rotary evaporator, and the residue was washed with 100 ml of water. Next, it was washed several times with 100 ml of methanol and then vacuum-dried to obtain 6 g of a styryl derivative (1a) (yield 40%). In addition, Table 2 shows the measurement results of the phase transition temperature of the styryl derivative (1a).
(Identification data of styryl derivative (1a))

G: Glass state, Sm1: Unidentified smectic phase other than smectic A phase and B phase, Sm2: Unidentified smectic phase other than smectic A phase and B phase, I: Isotropic liquid

{Reference Example 1}
A styryl derivative represented by the following general formula (A) was synthesized according to Japanese Patent Application Laid-Open No. 2004-6271.

Cr: Crystal, SmG: Smectic G phase, Smectic F phase, Smectic C phase, N: Nematic phase, I: Isotropic liquid

<Evaluation of rubbing treatment>
The styryl derivative (1a) obtained in Example 1 and the styryl obtained in Reference Example 1 were formed on the alignment film of a glass substrate on which a polyimide alignment film LX-1400 film manufactured by Hitachi Chemical DuPont was formed and rubbed. Each derivative was sandwiched. Next, this was placed on a heating device, heated to a temperature at which it becomes an isotropic liquid, cooled to room temperature (25 ° C.), and the transmitted light was observed with a polarizing microscope.
In the styryl derivative (1a) of Example 1, strong transmitted light was observed when rotated to 45 ° as shown in FIG. 6, and no transmitted light was observed when rotated further to 90 °. It was observed that the styryl derivative (1a) of Example 1 took a horizontal orientation with respect to the substrate at room temperature.
On the other hand, in the styryl derivative obtained in Reference Example 1, weak transmitted light was observed when rotated to 45 ° as shown in FIG. 6, and transmitted light was further observed when rotated to 90 °. From the results, it was confirmed that the styryl derivative of Reference Example 1 in the room temperature range had little horizontal alignment with respect to the substrate.

<Evaluation of charge transport ability>
Two glass substrates provided with ITO electrodes by vacuum film formation were provided with a gap (50 μm) with spencer particles so that the ITO electrodes face each other, and cells were created. The styryl derivative (1a) obtained in Example 1 was press-fitted into the cell. Next, a voltage of 5 V was applied, the temperature was gradually increased, and the current value at each temperature was measured. The result is shown in FIG.
Further, the styryl derivative (1a) obtained in Example 1 was injected into the cell under the condition of becoming an isotropic liquid. The mixture was naturally cooled to room temperature once to obtain a solid state generated by the phase transition of the smectic phase, and then the amount of current for each voltage at room temperature (25 ° C.) was measured. The result is shown in FIG.

{Reference Example 2}
Samples ((A1) and (A2)) having different R in the formula of the styryl derivative represented by the general formula (A) of Reference Example 1 were synthesized according to JP-A-2004-6271, respectively.

Cr; Crystal, SmG; Smectic G phase, SmF; Smectic F phase, SmC; Smectic C phase, N: Nematic, I; Isotropic liquid

Next, as in Example 1, two glass substrates provided with ITO electrodes by vacuum film formation were provided with a gap (15 μm) with spencer particles so that the ITO electrodes face each other, and a cell was created. did. 20 mg of a mixture containing equal amounts (1: 1 by weight) of the styryl derivative (A1) and styryl derivative (A2) prepared above was pressed into the cell.
Next, a voltage of 8 V was applied, the temperature was gradually increased, and the amount of current at each temperature was measured. The results are shown in Table 5 and FIG.
Further, 20 mg of a mixture containing equal amounts (1: 1 by weight) of the styryl derivative (A1) and the styryl derivative (A2) prepared above was poured into the cell under the condition of becoming an isotropic liquid, and once until the room temperature range After naturally cooling to obtain a solid state generated by the phase transition of the smectic phase, the current density at 30 ° C. was measured. The results are shown in Table 5.

30 ° C. shows the current density in the solid state, and 300 ° C. shows the current value in the liquid crystal state.

As a result of FIGS. 7 and 9, the liquid crystal temperature has a current value of 1000 times or more, and the current density of the solid body in the room temperature region is 1.0 × 10 ⁻⁴ μA / cm ² in Reference Example 1. In contrast, the styryl derivative of Example 1 was 8 μA / cm ² or more, which was 10,000 times or more.

{Example 2}
<Preparation process of aldehyde compound (2a-1)>

Using a 300 ml Erlenmeyer flask, the compound (a2-1) (1.5 × 10 ⁻² mol) and 4.02 g (3.0 × 10 ⁻² mol) of terephthalaldehyde were stirred in 100 ml of methanol, and the solution A Was prepared.
28 wt% sodium methoxide 2.89 g (1.5 × 10 ⁻² mol) was used as solution B, which was added dropwise to solution A, and reacted at 60 ° C. with stirring for 24 hours.
After completion of the reaction, the reaction solution was poured into 300 g of ice water, and then extracted with 300 ml of chloroform using a 1000 ml separatory funnel. Next, the extract was dehydrated with anhydrous sodium sulfate overnight.
This was filtered, and chloroform was removed under reduced pressure by an evaporator. 200 ml of hexane was added to the residue and heated to 65 ° C., followed by filtration to separate into a hexane soluble part and an insoluble part, and then purified by column chromatography.
Since the cis-trans isomer was mixed after purification, a small amount of iodine and p-xylene were added to the compound, and the mixture was refluxed at 120 ° C. for 4 hours under a nitrogen atmosphere. This was cooled to room temperature, filtered through 30 ml of cold hexane, and washed with 10 ml of cold methanol to obtain a trans aldehyde compound (2b-1).

Using a 500 ml two-necked flask, compound (a3-1) (20.06 mM) and 7.81 g (20.64 mM) of tetraethyl p-xylylene diphosphonate (a4) were dissolved in 50 ml of THF to prepare a solution A. Next, a solution obtained by dissolving 2.58 g (22.99 mM) of potassium tert-butoxide in 100 ml of THF was designated as solution B. Next, B liquid was dripped slowly into A liquid, and it reacted by stirring at room temperature (25 degreeC) for 5 hours.
After completion of the reaction, the reaction solution was concentrated with a rotary evaporator, 200 ml of methanol was added to the residue, and the soluble part was recovered and concentrated. This is extracted by adding 300 ml of toluene and 300 ml of saturated saline, and washed several times with 300 ml of distilled water. Thereafter, the oil layer was dehydrated with anhydrous sodium sulfate overnight. After dehydration, the mixture was filtered and concentrated with a rotary evaporator. To the next residue, 100 ml of hexane was added and filtered, and the hexane insoluble matter was recovered to obtain a phosphorus compound (3b-1).

Using a 100 ml Erlenmeyer flask, the aldehyde compound (2b-1) (1.9 × 10 ⁻⁹ mol) and the phosphorus compound (3b-1) (1.94 × 10 ⁻³ mol) were dissolved in 50 ml of THF. Potassium-t-butoxide (4.92 × 10 ⁻³ mol) was added thereto and reacted at room temperature under a nitrogen atmosphere for 17 hours.
After completion of the reaction, 4 ml of 36% hydrochloric acid was added to stop the reaction, the mixture was concentrated with a rotary evaporator, and the residue was washed with 50 ml of water. Next, it was washed twice with 50 ml of methanol and then vacuum-dried to obtain 1.30 g of a styryl derivative (1B-1).
Further, the obtained styryl derivative (1B-1) was sandwiched between two glass substrates, heated to a liquid crystal phase-isotropic liquid transition temperature or higher, and the transmitted light was observed with a polarizing microscope. Was confirmed to be a liquid crystalline compound having a smectic phase as a liquid crystal phase having a vertical alignment with respect to the substrate.

(Identification data of styryl derivative (1B-1))

{Example 3}
<Preparation process of styryl derivative (1C-1)>

The aldehyde compound (2b-1) (4 × 10 ⁻³ mol) and p-xylene bis- (triphenylphosphonium bromide) (3c) (2 × 10 ⁻³ mol) were dissolved in 50 ml of THF in a 100 ml Erlenmeyer flask. Potassium-t-butoxide (1 × 10 ⁻² mol) was added thereto and reacted at room temperature (25 ° C.) under a nitrogen atmosphere for 18 hours.
After completion of the reaction, 4 ml of 36% hydrochloric acid was added to stop the reaction, the mixture was concentrated with a rotary evaporator, and the residue was washed with 50 ml of water. Next, it was washed twice with 50 ml of methanol and then dried under vacuum to obtain a styryl derivative (1C-1).
Further, the obtained styryl derivative (1C-1) was sandwiched between two glass substrates, heated to a liquid crystal phase-isotropic liquid transition temperature or higher, and the transmitted light was observed with a polarizing microscope. Was confirmed to be a liquid crystalline compound having a smectic phase as a liquid crystal phase having a vertical alignment with respect to the substrate.
(Identification data of styryl derivative (1C-1))

{Example 4}
<Preparation process of styryl derivative (1C-1)>

Phosphorus compound (3b-1) (4 × 10 ⁻³ mol) and terephthalaldehyde (2a) (2 × 10 ⁻³ mol) were dissolved in 50 ml of THF in a 100 ml Erlenmeyer flask. Potassium-t-butoxide (1 × 10 ⁻² mol) was added thereto and reacted at room temperature (25 ° C.) under a nitrogen atmosphere for 18 hours.
After completion of the reaction, 4 ml of 36% hydrochloric acid was added to stop the reaction, the mixture was concentrated with a rotary evaporator, and the residue was washed with 50 ml of water. Next, it was washed twice with 50 ml of methanol and then dried under vacuum to obtain a styryl derivative (1C-1).
The obtained styryl derivative was analyzed by ¹ H-NMR and FT-IR. As a result, the same pattern as in Example 3 was shown.
Further, the obtained styryl derivative (1C-1) was sandwiched between two glass substrates, heated to a liquid crystal phase-isotropic liquid transition temperature or higher, and the transmitted light was observed with a polarizing microscope. Was confirmed to be a liquid crystalline compound having a smectic phase as a liquid crystal phase having a vertical alignment with respect to the substrate.

{Example 5}
<Preparation process of aldehyde compound (2b-2)>

The phosphorus compound (3a-1) was synthesized in the same manner as in Example 1, except that 1-bromodecane was used instead of 1-bromododecane (5a) in the preparation step of the compound (6a) of Example 1.
Using a 300 ml Erlenmeyer flask, 7.9 g (0.011 mol) of compound (3a-1) and 2.3 g (0.017 mol) of terephthalaldehyde (2a) were dissolved in 50 ml of tetrahydrofuran (solution A). Separately, 1.9 g (0.017 mol) of potassium t-butoxide was dissolved in 100 ml of tetrahydrofuran (solution B).
The liquid B was added dropwise to the liquid A at room temperature (25 ° C.), and the reaction was further performed by stirring overnight at room temperature (25 ° C.) in a nitrogen atmosphere.
After completion of the reaction, tetrahydrofuran was removed under reduced pressure with a rotary evaporator to obtain a residue. Next, 150 ml of methanol was added to the residue, and a methanol-soluble part was obtained by filtration. This was removed under reduced pressure and then extracted with 200 ml of diethyl ether. Next, it was washed several times with water, and anhydrous sodium sulfate was added to the obtained ether layer and dehydrated overnight. Next, it was filtered to remove anhydrous sodium sulfate, and diethyl ether was removed under reduced pressure with a rotary evaporator to obtain an aldehyde compound (2b-2).
<Preparation process of styryl derivative (1C-2)>

Using a 100 ml Erlenmeyer flask, 1.5 g (2.2 mM) of aldehyde compound (2b-2) and 0.42 g (1.1 mM) of phosphorus compound (a4) were dissolved in 30 ml of tetrahydrofuran. Next, 1.21 g (10.78 mM) of potassium t-butoxide was added thereto, and the reaction was performed at room temperature (25 ° C.) in a nitrogen atmosphere for 17 hours.
After completion of the reaction, 5 ml of 36% hydrochloric acid was added to stop the reaction, the mixture was concentrated with a rotary evaporator, and the residue was washed with 100 ml of water. Next, it was washed twice with 50 ml of methanol and then dried under vacuum to obtain 0.5 g of a styryl derivative (1C-1).
In addition, Table 9 shows the measurement results of the phase transition temperature of the styryl derivative (1C-2).
(Identification data of styryl derivative (1C-2))

G: Glass state, Sm: Smectic phase, I: Isotropic liquid

<Evaluation of solubility>
The styryl derivatives ((1a), (1C-2)) obtained in Example 1 and Example 5 and the styryl derivatives ((A), (A1), (A2)) obtained in Reference Examples 1-2 were used. The solubility of styryl derivatives in hexane after being left at 25 ° C. for 24 hours is very well dissolved (◯), not very well soluble (Δ), and added to hexane so that the concentration becomes 50 mg / ml and 500 mg / ml. Visual evaluation was made in three stages of no melting (x). The results are shown in Table 10.

1a; Glass substrate 2a; Electrode 3a; Conductive liquid crystal layer 2b; Electrode 1b; Glass electrode 4; Spencer 5; Voltage application means b1; Substrate b2; Anode b3; Buffer layer b4; Layer b7; gate b8; source b9; drain b10; insulating film b11; channel portion

Claims

A liquid crystalline styryl derivative represented by the following general formula (1):

(Wherein R 1 represents an alkyl group, and n represents an integer of 1 to 3)
2. The liquid crystalline styryl derivative according to claim 1, wherein n in the formula (1) is 1.
3. The liquid crystalline styryl derivative according to claim 1, wherein R 1 in the formula (1) is an alkyl group having 4 to 18 carbon atoms.
The following general formula (2a)

An aldehyde compound represented by the following general formula (3a)

(Wherein R 1 is as defined above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1A):

The method for producing a liquid crystalline styryl derivative according to claim 1, wherein R 1 is as defined above.
The following general formula (2b)

(Wherein R 1 is as defined above), and the following general formula (3b)

(Wherein R 1 is as defined above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1B)

The method for producing a liquid crystalline styryl derivative according to claim 1, wherein R 1 is as defined above.
The following general formula (2b)

(Wherein R 1 is as defined above) and the following general formula (3c)

The following general formula (1C) characterized by reacting with a phosphorus compound represented by the formula

The method for producing a liquid crystalline styryl derivative according to claim 1, wherein R 1 is as defined above.
The following general formula (2a)

An aldehyde compound represented by the following general formula (3b)

(Wherein R 1 has the same meaning as described above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1C)

The method for producing a liquid crystalline styryl derivative according to claim 1, wherein R 1 is as defined above.
The following general formula (2b)

(Wherein R 1 is as defined above) and the following general formula (a4)

(Wherein R 1 has the same meaning as described above, Et represents an ethyl group) and a phosphorus compound represented by the following general formula (1C)

The method for producing a liquid crystalline styryl derivative according to claim 1, wherein R 1 is as defined above.
A conductive liquid crystal material comprising the liquid crystalline styryl derivative according to any one of claims 1 to 3.
An organic semiconductor element comprising the conductive liquid crystal material according to claim 9.
The organic semiconductor element according to claim 10, wherein a thin film using the conductive liquid crystal material according to claim 9 is formed between electrodes provided with a pair of electrodes.
An organic semiconductor element has three electrodes of a gate, a source and a drain, an insulating film formed so as to cover the gate electrode, and a channel portion which conducts between the source and drain electrodes formed outside the insulating film. The organic semiconductor device according to claim 10, wherein the channel portion is a thin film transistor comprising a layer made of the conductive liquid crystal material according to claim 9.
The organic semiconductor element according to claim 12, wherein the insulating film is made of polyimide, and the insulating film is rubbed to enhance the orientation of the conductive material of the outer layer.