JPH07188095A - Tolan derivative compound, liquid crystal material and liquid crystal display element containing the same - Google Patents

Abstract

PURPOSE:To obtain a new tolan derivative compound useful as a liquid crystal display element having a high DELTAn value, excellent chemical stability and high- speed responsiveness. CONSTITUTION:A compound of formula I (R<1> is a 1-8C straight-chain alkyl; Z<1> to Z<5> each is H or F; with the proviso that the number of F is one or two, and only when the whole Z<1> to Z<4> are H, Z<5> is a 1-12C straight-chain alkoxy or a nonsubstituted phenyl) such as a compound of formula II. The compound of formula I is obtained by reacting a compound of formula III with a compound of formula IV (X is an eliminable group). The compound of formula III is a new compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel tolan derivative compound, a liquid crystal material containing the same, and a liquid crystal display device.

[0002]

2. Description of the Related Art Liquid crystal display devices include clocks, calculators,
In recent years, it has been used in various applications such as measuring machines, copiers, cameras, etc., but it has various characteristics such as low voltage drive, high speed response, high contrast ratio, low temperature response, wide operating temperature range, and chemical stability. Improving performance is required. However, improving any one of them tends to sacrifice other properties. Therefore, by mixing a liquid crystal material or a non-liquid crystal material having different properties, a liquid crystal material having a desired property can be obtained. The current situation is to use it.

At present, for a TN (twisted nematic) liquid crystal display element, a high-speed response for moving images is under study. In order to realize a high-speed response, it is known that the response time is further shortened by making the thickness dμm (hereinafter abbreviated as d value) of the liquid crystal display element thinner. However, if the d value is too small, problems such as the generation of interference fringes that cause a deterioration in the appearance of the liquid crystal display element occur, and therefore the refractive anisotropy value Δn (hereinafter abbreviated as Δn value)
It is necessary to set the Δnd value, which is the product of d and the d value, to a certain value.

In order to obtain the set specific value of Δnd, the d value can be reduced and the response time can be shortened by using a liquid crystal material having a large Δn value. Therefore, the use of a liquid crystal material having a large Δn value is extremely important for producing a liquid crystal display element having a high response speed without impairing the appearance of the liquid crystal display element.

As described above, among the various characteristics required for the liquid crystal material used in the liquid crystal display element, a particularly important physical property is a large Δn value and a chemical stability. As a liquid crystal material having a large Δn value, a tolan derivative compound as shown below (JP-A-60-152427) is used.
JP, JP-A-61-260031, JP, JP-A-63
-310838, JP-A-3-67058,
JP-A-4-82854, JP-A-5-43503, etc.) are known.

[0006]

[Chemical 3]

However, the Δn value of these tolan derivative compounds is not sufficient, and a liquid crystal material having a large Δn value is desired.

As a raw material for obtaining the above-mentioned tolan derivative compound, phenylacetylene compounds as shown below are known.

[0009]

[Chemical 4]

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel tolan derivative compound which has good compatibility with other liquid crystal materials and is chemically stable, and which contains this novel tolan derivative compound. A liquid crystal material having a large n value and being chemically stable, and a liquid crystal display element using the liquid crystal material.

[0011]

Means for Solving the Problems As a result of diligent studies, the inventors of the present invention found a novel tolan derivative compound that achieves the above object and a novel phenylacetylene compound as a raw material thereof, and identified the novel tolan derivative compound. A liquid crystal material and a liquid crystal display element to be contained were obtained, and the present invention was completed.

That is, the present invention uses a phenylacetylene compound represented by the general formula <B> as a raw material and has the general formula <
A tolan derivative compound represented by A>, and a liquid crystal material and a liquid crystal display device containing the novel tolan derivative compound.

[0013]

[Chemical 5]

In the formula, R ¹ represents a linear alkyl group having 1 to 8 carbon atoms.

Examples of the linear alkyl group having 1 to 8 carbon atoms represented by R ¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n
An octyl group.

[0016]

[Chemical 6]

In the formula, R ¹ represents a linear alkyl group having 1 to 8 carbon atoms. Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are hydrogen atoms or fluorine atoms, and the number of fluorine atoms is 1 or 2. Alternatively, Z ⁵ represents a straight-chain alkoxy group having 1 to 12 carbon atoms or an unsubstituted phenyl group only when Z ¹ , Z ² , Z ³ and Z ⁴ are all hydrogen atoms.

Examples of the linear alkyl group having 1 to 8 carbon atoms represented by R ¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n
An octyl group.

The substitution positions of the fluorine atom in Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ include the 2-position, 3-position and 4-position in the case of one substitution, and the substitution positions of two substitutions In this case, in terms of raw material supply and price, the 2nd, 4th, 3rd, 4th, and 3rd are given.

When Z ¹ , Z ² , Z ³ and Z ⁴ are all hydrogen atoms, the linear alkoxy group having 1 to 12 carbon atoms (Z ⁵ ) is a methoxy group, ethoxy group, n-propoxy group, n -Butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-
Examples thereof include nonyloxy group, n-decyloxy group, n-undecyloxy group and n-dodecyloxy group.

The tolan derivative compound represented by the general formula <A> of the present invention is obtained by the following reaction.

[0022]

[Chemical 7]

In the formula, X represents a bromine atom or an iodine atom, TEA represents triethylamine, and DEA represents diethylamine. As a solvent for the reaction <1> and the reaction <3>,
A basic solvent such as triethylamine or diethylamine and an aromatic hydrocarbon solvent such as benzene or toluene are used in combination.

Reaction <1> General formula <E obtained by Friedel-Crafts reaction in the presence of bis (triphenylphosphine) palladium dichloride (hereinafter abbreviated as palladium catalyst) and cuprous iodide.
> In a basic solvent such as triethylamine and diethylamine and an aromatic hydrocarbon solvent such as benzene and toluene at a temperature of 20 to 100 ° C. and 1-methyl-1-butyn-3-ol After reacting for ~ 24 hours, add to dilute hydrochloric acid, extract with solvent, wash with water, dehydrate and concentrate,
Purified by column chromatography using an alumina column or silica gel column or vacuum distillation,
A compound represented by the general formula <D> is obtained.

Reaction <2> In the presence of sodium hydride, the compound represented by the general formula <D> obtained in reaction <1> is gradually heated at room temperature in a toluene solvent to form acetone. After refluxing toluene, the reaction is carried out until the boiling point of toluene (temperature: 110 ° C) is reached, followed by filtration, washing the filtrate with water, dehydration and concentration, and column chromatography using an alumina column or vacuum distillation. To obtain a phenylacetylene compound represented by the general formula <B> of the present invention.

Reaction <3> Reaction <2> in the presence of a palladium catalyst and cuprous iodide
The phenylacetylene compound represented by the general formula <B> and the compound represented by the general formula <C> obtained in the above are added in a basic solvent such as triethylamine or diethylamine and an aromatic hydrocarbon solvent such as toluene, Temperature 10 ℃ -100 ℃, 1-2
After reacting for 4 hours, the mixture was added to diluted hydrochloric acid, extracted with a solvent, washed with water, dehydrated and concentrated, and then purified by column chromatography using an alumina column or a silica gel column or vacuum distillation to give a compound represented by the general formula < A tolan derivative compound represented by A> is obtained.

General formula <C used in reaction <3>
Among the compounds represented by>, examples having a phenyl group and an alkoxy group are shown below.

[0028]

[Chemical 8]

Furthermore, compounds in which the bromine atom of the above-mentioned compounds is replaced with an iodine atom are also included.

Among the compounds represented by the general formula <C> used in the reaction <3>, examples having one or two fluorine atoms are shown below.

[0031]

[Chemical 9]

Furthermore, compounds in which the bromine atom of the above-mentioned compounds is replaced with an iodine atom are also included.

The phenylacetylene compound represented by the general formula <B> of the present invention obtained as described above is exemplified below. The present invention is not limited to these examples. Further, the compound No. is commonly used in the examples.

[0034]

[Chemical 10]

Further, similarly obtained general formula <A of the present invention
The tolan derivative compound represented by> is illustrated below.
The present invention is not limited to these examples. Further, the compound No. is commonly used in the examples.

[0036]

[Chemical 11]

[0037]

[Chemical 12]

The tolan derivative compound represented by the general formula <A> of the present invention has excellent compatibility with other liquid crystal materials and is chemically stable. The value can be increased.

The liquid crystal material of the present invention has the general formula <A of the present invention.
> Is obtained by blending one or more of the tolan derivative compounds represented by> with another liquid crystal material, and the Δn value is large,
It is chemically stable.

The compounding amount of the tolan derivative compound represented by the general formula <A> of the present invention to another liquid crystal material is 0.5 to 50% by weight, preferably 5 to 50% by weight based on the total weight of the liquid crystal material.
Is.

The liquid crystal display device using the liquid crystal material of the present invention has excellent characteristics that the response speed is fast and there are no interference fringes that impair the appearance.

Further, the phenylacetylene compound represented by the general formula <B> of the present invention is not only a raw material for obtaining the tolan derivative compound represented by the general formula <A> of the present invention but also other than the present invention. It also serves as a raw material for obtaining the novel tolan derivative compound.

In addition, the phenylacetylene compound represented by the general formula <B> of the present invention can be used as a raw material other than the liquid crystal material, like the conventional phenylacetylene compound. For example, by polymerization, polyacetylene-based conductive polymer, polymer organic magnetic material, etc., acetylene alcohol as a host material for optical resolution, as a tolan analog for electrophotographic photoreceptors, anti-inflammatory agents, and fluorescence of chemiluminescence. It can be applied to the body, etc.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.

Example 1 <Example 1-1> 100 g of bromobenzene was added to carbon disulfide 2
Dissolve in 40 ml, add 85 g of anhydrous aluminum chloride, and
While stirring at 40 ° C., 59 g of propionyl chloride was added dropwise, the reaction was continued for 1 hour, and then carbon disulfide was distilled off to obtain a reaction mixture. The obtained reaction mixture was mixed with 10 wt.
% Aqueous solution of hydrochloric acid, and extracted with toluene. 10 wt%
After washing with an aqueous solution of sodium hydroxide, the mixture was washed with water until it became neutral. After dehydration with anhydrous sodium sulfate, toluene was distilled off, and 108 g of colorless crystals of 4'-bromopropionphenone.
(Melting point: 45-48 ° C.) was obtained.

The obtained 4'-bromopropionphenone 1
6.9g, palladium catalyst 0.37g and cuprous iodide 0.13g
Was dissolved in 15 ml of dry benzene and 15 ml of triethylamine, and 3-methyl-1-butyne-3 was stirred with stirring at room temperature.
-Drop 7g of all, heat to 70 ℃ in 30 minutes,
The reaction was continued for 20 hours. Then, add to 300 ml of dilute hydrochloric acid, confirm that the aqueous layer is weakly acidic, extract the oil layer with benzene, wash with water until neutral, dehydrate with anhydrous sodium sulfate, then distill off benzene, Purification by column chromatography using an alumina column gave 18.4 g of the oily compound shown below.

[0047]

[Chemical 13]

8.6 g of the compound obtained and 150 ml of toluene
To the above, 0.14 g of sodium hydride was added, and the mixture was stirred at room temperature for 30 minutes, and then gradually heated to reflux the generated acetone and toluene until the boiling point of toluene reached 110 ° C., and then filtered off. The filtrate was washed with water, dehydrated, concentrated, and purified by column chromatography using an alumina column to obtain 18.4 g of colorless crystals. According to infrared spectroscopic analysis and NMR spectrum, this product had 4-propionylphenylacetylene, compound NO.2 (melting point: 61-62).
℃).

<Example 1-2> 4-iodoanisole
4.7 g, palladium catalyst 0.02 g and cuprous iodide 0.03 g
Was dissolved in 16 ml of triethylamine and 16 ml of dry benzene and stirred at room temperature with stirring to obtain 4-
3.2g of propionylphenylacetylene and 5m of benzene
The solution (1) was added dropwise, the temperature was raised to 90 ° C. in 30 minutes, and the reaction was continued for 5 hours. Then, the mixture was added to dilute hydrochloric acid, extracted with benzene, and washed with water until it became neutral. After dehydration with anhydrous sodium sulfate, benzene was distilled off and the residue was purified by column chromatography using a silica gel column and recrystallized several times with ethanol to obtain 3.1 g of colorless crystals.

Infrared spectroscopic analysis of the obtained compound showed characteristic absorption of tolan at a wavelength of 2230 cm ^-1, and from the NMR spectrum thereof, 4-propionyl-4'-methoxytran, compound No. 11 (melting point: 111 ℃).

Example 2 In Example 1-2, 4-iodobiphenyl 5.6 g,
0.02 g of palladium catalyst and 0.03 g of cuprous iodide were dissolved in 16 ml of diethylamine and 32 ml of toluene, and a solution of 3.2 g of 4-propionylphenylacetylene obtained in Example 1-1 and 5 ml of toluene was stirred while stirring at room temperature. 4.0 g of colorless crystals in the same manner as in Example 1-2 except that the dropwise addition was performed.
Got

The compound obtained was analyzed by infrared spectroscopy to give 22
Characteristic absorption of tolan was observed at 10 cm ^−1, and by NMR spectrum, 4-propionyl-4′-phenyltolan, compound No. 13 (liquid crystal transition point (CN): 156 ° C.,
Clearing point (NI): 160 ° C).

Example 3 In Example 1-2, 2-fluoroiodobenzene 3.
0 g of palladium catalyst, 0.03 g of palladium catalyst and 0.03 g of cuprous iodide were dissolved in 30 ml of diethylamine and 30 ml of toluene, and 2.2 g of 4-propionylphenylacetylene obtained in Example 1-1 and 5 ml of toluene were stirred with stirring at room temperature. Colorless crystals were obtained in the same manner as in Example 1-2 except that the solution was added dropwise.
2.0 g was obtained.

The obtained compound showed characteristic absorption of tolan at a wavelength of 2230 cm ^-1 by infrared spectroscopic analysis, and 4-propionyl-2'-fluorotolan, compound NO.14 (melting point: 100 ° C.) by NMR spectrum. )Met.

Example 4 <Example 4-1> 100 g of bromobenzene was added to carbon disulfide 2
Dissolve in 40 ml, add 85 g of anhydrous aluminum chloride, and
77.1 g of valeroyl chloride was added dropwise with stirring at 40 ° C., and the reaction was continued for 1 hour, then carbon disulfide was distilled off to obtain a reaction mixture. 10 wt% of the obtained reaction mixture
The mixture was added to a hydrochloric acid ice solution, extracted with toluene, washed with a 10 wt% sodium hydroxide aqueous solution, and then washed with water. After dehydration with anhydrous sodium sulfate, toluene was distilled off to obtain 123 g of colorless crystals of 4'-bromovalerophenone (melting point: 34 to 36 ° C).

10 g of 4'-bromovalerophenone, 0.2 g of palladium catalyst and 0.06 g of cuprous iodide were dissolved in 10 ml of diethylamine and 10 ml of toluene, and 3-methyl-1-butyn-3-one was stirred with stirring at room temperature. 4g was dropped,
The temperature was raised to 90 ° C. in 30 minutes and the reaction was continued for 5 hours.
Then, add to dilute hydrochloric acid, extract with toluene, wash with water, dehydrate with anhydrous sodium sulfate, and then distill off toluene,
Purification by column chromatography using a silica gel column gave 9.12 g of the following compound as an oil.

[0057]

[Chemical 14]

9.12 g of the obtained compound and 27 of dry toluene
Sodium hydride (0.14 g) was added to 0 ml, and the mixture was stirred at room temperature for 30 minutes, then gradually heated to reflux the acetone and toluene produced, until the boiling point of toluene reached 110 ° C, and then filtered off. Then, the filtrate was washed with water, dehydrated and concentrated, and purified by column chromatography using an alumina column to obtain 4.9 g of colorless crystals. According to infrared spectroscopic analysis and NMR spectrum, this product is 4-valeroylphenylacetylene, compound NO.4 (melting point: 58-60 ° C)
Met.

<Example 4-2> 4-Iodoanisole
4.7 g, palladium catalyst 0.02 g and cuprous iodide 0.03 g
Was dissolved in 16 ml of triethylamine and 16 ml of dry toluene, and the mixture obtained in Example 4-1 was stirred while stirring at room temperature.
Valeroyl phenylacetylene 3.8g and toluene 5ml
Solution was added dropwise and heated to a temperature of 90 ° C for 30 minutes, then 5
Reacted for hours. Then, the mixture was added to diluted hydrochloric acid, extracted with toluene, and washed with water. After dehydration with anhydrous sodium sulfate,
After removing toluene by distillation and purifying by column chromatography using a silica gel column, recrystallization was performed several times with ethanol to obtain 4.4 g of colorless crystals.

Infrared spectroscopic analysis of the obtained compound showed characteristic absorption of tolan at a wavelength of 2230 cm ^-1, and NMR spectrum revealed that 4-valeroyl-4'-methoxytolan, compound NO.17 (melting point: 99 ℃).

Example 5 In Example 4-2, 6.8 g of 4-n-dodecyloxybromobenzene, 0.02 g of palladium catalyst and 0.03 g of cuprous iodide were added to 16 ml of triethylamine and 16 ml of dry toluene.
A solution of 3.8 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene was added dropwise with stirring at room temperature, and the mixture was heated to a temperature of 90 ° C. for 30 minutes and allowed to react for 20 hours. 5.3 g of colorless crystals was obtained in the same manner as in Example 4-2 except that the above was used.

Infrared spectroscopic analysis of the obtained compound showed a characteristic absorption of tolan at a wavelength of 2230 cm ^-1, and the NMR spectrum thereof revealed that 4-valeroyl-4'-n-dodecyloxytran and compound No. 19 ( Liquid crystal transition point (CN): 1
02 ° C, clearing point (N-I): 118 ° C).

Example 6 In Example 4-2, 4.7 g of 4-bromobiphenyl,
0.02 g of palladium catalyst and 0.03 g of cuprous iodide were dissolved in 16 ml of diethylamine and 32 ml of toluene, and a solution of 3.8 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene while stirring at room temperature. 4 g of colorless crystals was obtained in the same manner as in Example 4-2, except that was added dropwise.

Infrared spectroscopic analysis of the obtained compound showed characteristic absorption of tolan at a wavelength of 2210 cm ^-1, and NMR spectrum showed 4-valeroyl-4'-phenyltolan, compound No. 20 (liquid crystal transition point). (C−N): 145 ° C., clearing point (N−I): 176 ° C.).

Example 7 In Example 4-2, 4-fluoroiodobenzene 3.
0 g of palladium catalyst, 0.01 g of cuprous iodide and 0.01 g of cuprous iodide were dissolved in 15 ml of diethylamine and 15 ml of toluene, and 2.5 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene were stirred at room temperature. Colorless crystals were obtained in the same manner as in Example 4-2 except that the solution of 2. was added dropwise.
3 g was obtained.

The obtained compound was analyzed by infrared spectroscopy and NM.
According to the R spectrum, it was 4-valeroyl-4′-fluorotran, compound No. 21 (melting point: 90 ° C.).

Example 8 In Example 4-2, 3-fluoroiodobenzene 3.
0 g of palladium catalyst, 0.01 g of cuprous iodide and 0.01 g of cuprous iodide were dissolved in 15 ml of diethylamine and 15 ml of toluene, and 2.5 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene were stirred at room temperature. Colorless crystals were obtained in the same manner as in Example 4-2 except that the solution of 2. was added dropwise.
6 g was obtained.

The obtained compound was analyzed by infrared spectroscopy and NM.
According to the R spectrum, it was 4-valeroyl-3′-fluorotran, compound NO.22 (melting point: 84 ° C.).

Example 9 In Example 4-2, 3.3 g of 3,4-difluoroiodobenzene, 0.01 g of palladium catalyst and 0.0 g of cuprous iodide were used.
Dissolve 1 g in 15 ml of diethylamine and 15 ml of toluene,
2.0 g of colorless crystals were obtained in the same manner as in Example 4-2, except that the solution of 2.5 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene was added dropwise with stirring at room temperature. It was

The obtained compound was analyzed by infrared spectroscopy and NM.
By R spectrum, it was 4-valeroyl-3 ′, 4′-difluorotran, compound NO.23 (melting point: 78 ° C.).

Example 10 In Example 4-2, 3.3 g of 2,4-difluorobromobenzene, 0.01 g of palladium catalyst and 0.09 cuprous iodide were used.
Dissolve 1 g in 15 ml of diethylamine and 15 ml of toluene,
2.4 g of colorless crystals was obtained in the same manner as in Example 4-2, except that the solution of 2.5 g of 4-valeroylphenylacetylene obtained in Example 4-1 and 5 ml of toluene was added dropwise with stirring at room temperature. It was

The obtained compound was analyzed by infrared spectroscopy and NM.
By R spectrum, it was 4-valeroyl-2 ′, 4′-difluorotran, compound NO.24 (melting point: 88 ° C.).

Example 11 In Example 4-2, 3.3 g of 3,5-difluoroiodobenzene, 0.01 g of palladium catalyst and 0.09 of cuprous iodide were used.
Dissolve 1 g in 15 ml of diethylamine and 15 ml of toluene,
2.8 g of colorless crystals was obtained in the same manner as in Example 4-2, except that the solution of 4-valeroylphenylacetylene obtained in Example 4-1 (2.5 g) and toluene (5 ml) was added dropwise with stirring at room temperature. It was

The obtained compound was analyzed by infrared spectroscopy and NM.
By R spectrum, it was 4-valeroyl-3 ′, 5′-difluorotran, compound NO.25 (melting point: 75 ° C.).

Example 12 <Example 12-1> In Example 1-1, pelargonyl chloride 11 was used instead of 59 g of propionyl chloride.
A colorless liquid 4-pelargonylphenylacetylene and compound N were prepared in the same manner as in Example 1 except that 3.25 g was used.
I got 0.8.

Example 12-2 In Example 1-2, 4.7 g of 4-iodoanisole and 0.02 of palladium catalyst were used.
g and 0.03 g of cuprous iodide were dissolved in 16 ml of diethylamine and 16 ml of toluene, and the mixture of Example 12 was stirred at room temperature.
4-Peralgonylphenylacetylene obtained in -1.
4.3 g of colorless crystals was obtained in the same manner as in Example 1-2, except that a solution of 8 g and 10 ml of toluene was added dropwise.

Infrared spectroscopic analysis of the obtained compound showed characteristic absorption of tolan at a wavelength of 2210 cm ^-1, and NMR spectrum showed that 4-pelargonyl-4'-methoxytolan, compound No. 28 (liquid crystal transition point). (CN): 98 ° C,
Clearing point (N-I): 105 ° C).

Example 13 In Example 1-2, 4-fluoroiodobenzene 3.
0 g of palladium catalyst, 0.01 g of cuprous iodide and 0.01 g of cuprous iodide were dissolved in 10 ml of diethylamine and 10 ml of toluene, and stirred at room temperature with 3.3 g of 4-pelargonylphenylacetylene obtained in Example 12-1 and 5 ml of toluene. 3.0 g of colorless crystals was obtained in the same manner as in Example 1-2, except that the solution of 1 was added dropwise.

The obtained compound was analyzed by infrared spectroscopy and NM.
According to the R spectrum, it was 4-pelargonyl-4′-fluorotran, compound No. 30 (melting point: 91 ° C.).

Example 14 <Example 14-1> In the same manner as in Example 1-1, except that 65 g of acetic anhydride was used in place of 59 g of propionyl chloride in Example 1-1, 4-color colorless crystals were prepared. Acetylphenylacetylene, compound NO.1 (melting point: 51-54
C) was obtained.

Example 14-2 4.7 g of 4-iodoanisole, 0.02 g of palladium catalyst and cuprous iodide 0.03
Example 1-2 except that 16 g of diethylamine was dissolved in 16 ml of toluene and 16 ml of toluene was added and the solution of 4.8 g of 4-acetylphenylacetylene obtained in Example 14-1 and 10 ml of toluene was added dropwise while stirring at room temperature. In the same manner, 4.3 g of colorless crystals was obtained.

Infrared spectroscopic analysis of the obtained compound showed characteristic absorption of tolan at a wavelength of 2210 cm ^-1, and by NMR, 4-acetyl-4'-methoxytran, compound N was obtained.
It was 0.9 (melting point: 120 ° C).

Example 15 Commercially available liquid crystal material ZLI-1132 (manufactured by Merck & Co., Δn value =)
0.138) 90 wt% of the compound No. 11 obtained in Example 1 was blended at 10 wt% to obtain a liquid crystal material. Table 1 shows Δn values of the obtained liquid crystal materials.

Examples 16 and 17 Liquid crystal materials were obtained in the same manner as in Example 15, except that the compounding amount of the compound No. 11 was 5% by weight and 50% by weight. Table 1 shows Δn values of the obtained liquid crystal materials.

Examples 18 to 32 In Example 15, instead of the compound No. 11, Table 1 was used.
Liquid crystal materials were obtained by using the compounds shown in to. Tables 1 to 3 show Δn values of the obtained liquid crystal materials.

Comparative Example A liquid crystal material was obtained by blending 50% by weight of a commercially available liquid crystal material ZLI-1132 with 50% by weight of 4-pentyl-4′-methoxytran, which is an existing tolan derivative compound. The Δn value of the obtained liquid crystal material was 0.145. The results are shown in Table 3.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

The novel tolan derivative compound of the present invention has good compatibility with other liquid crystal materials and is chemically stable. The liquid crystal material obtained by blending the novel tolan derivative compound of the present invention has a large Δn value and is chemically stable,
A liquid crystal display device having excellent characteristics can be obtained. In addition, the novel phenylacetylene compound of the present invention can be used not only as a raw material for the tolan derivative compound of the present invention but also as a raw material for other compounds, and various applications are considered.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G02F 1/13 500

Claims (10)

[Claims] 1. A tolan derivative compound represented by the general formula <A>. [Chemical 1] (In the formula, R ¹ represents a linear alkyl group having 1 to 8 carbon atoms. Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are hydrogen atoms or fluorine atoms, and the fluorine atom is 1 Or Z ^2. Alternatively, Z ⁵ represents a linear alkoxy group having 1 to 12 carbon atoms or an unsubstituted phenyl group only when Z ¹ , Z ² , Z ³ and Z ⁴ are all hydrogen atoms. ) 2. The tolan derivative compound represented by the general formula <A> according to claim 1, wherein Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are hydrogen atoms or fluorine atoms, and fluorine atoms are included. Is a tol derivative compound having 1 or 2. 3. The tolan derivative compound represented by the general formula <A> according to claim 1, wherein Z ¹ , Z ² , Z ³ and Z ⁴ are hydrogen atoms, and Z ⁵ has 1 to 12 carbon atoms. A tolan derivative compound which is a straight-chain alkoxy group or an unsubstituted phenyl group. 4. A phenylacetylene compound represented by the general formula <B>, which is a raw material for the tolan derivative compound according to any one of claims 1 to 3. [Chemical 2] (In the formula, R ¹ represents a linear alkyl group having 1 to 8 carbon atoms.) 5. A liquid crystal material containing one or more of the tolan derivative compounds according to claim 1 in an amount of 0.5 to 50% by weight based on the total weight of the liquid crystal material. 6. A liquid crystal material containing one or more tolan derivative compounds according to claim 1 in an amount of 5 to 50% by weight based on the total weight of the liquid crystal material. 7. A liquid crystal display device using the liquid crystal material according to claim 5. 8. A liquid crystal display device using the liquid crystal material according to claim 6. 9. A method for producing a phenylacetylene compound represented by formula <B>. 10. A process for producing a tolan derivative compound represented by the general formula <A>, which comprises a phenylacetylene compound represented by the general formula <B> as an intermediate.