JPH0816158B2 - Liquid crystal copolymer and its manufacturing method, diene compound used in its manufacturing method and its manufacturing method - Google Patents

Description

The present invention relates to a novel liquid crystalline copolymer and a method for producing the same, as well as a diene compound used in the production thereof and a method for producing the same. More specifically, the present invention relates to a novel liquid crystalline copolymer that exhibits ferroelectricity even near room temperature, has a fast response speed to changes in an external electric field so as to be capable of displaying moving images, and can be advantageously used as a display element for a large screen or a curved screen, and a method for producing the same, as well as a diene compound used in the production thereof and a method for producing the same, which are useful in the field of optoelectronics, particularly as display elements for calculators, clocks, etc., electro-optical shutters, electro-optical diaphragms, optical modulators, optical path changeover switches for optical communication, memories, liquid crystal printer heads, variable focal length lenses, etc.

BACKGROUND ART Display elements using low-molecular-weight liquid crystals have been widely used in digital displays for calculators, clocks, and other devices. In these applications, conventional low-molecular-weight liquid crystals are typically sandwiched between two glass substrates with the spacing controlled to the micron order. However, such spacing adjustment has been impossible for large screens and curved screens. One way to solve this problem has been to polymerize the liquid crystal, making it moldable (J.
Polym.,Sci.,Polym.,Lett.,Ed. 13 , 243 (1975),Polym.,
Bull., 6 , 309 (1982), JP-A-56-21479, etc.).

However, these polymer liquid crystals have the drawback that the polymer itself does not exhibit liquid crystal properties at room temperature and must be heated in a temperature range above the glass transition temperature and below the clearing temperature to become liquid crystal.

In Japanese Patent Laid-Open Publication No. 63-99204, the synthesis of a polyacrylate-based ferroelectric polymer liquid crystal was reported, which was found to exhibit superior performance to the above-mentioned polymer liquid crystals. However, even this side-chain polymer liquid crystal still has problems with response speed and usable temperature range.

In addition, Japanese Patent Laid-Open No. 63-254529 discloses a polyether-based ferroelectric polymer liquid crystal obtained by polymerizing an epoxy monomer (for example, a compound represented by the following formula: (wherein s represents an integer of 1 to 30) Although this side-chain type polymer liquid crystal has the advantage of responding to an external electric field stimulus over a wide temperature range, including around room temperature, its response speed is slow and is not yet sufficient for practical use.

An object of the present invention is to provide a novel polymer liquid crystal which exhibits strong induction over a wide temperature range including room temperature and also responds quickly to an external electric field.

Another object of the present invention is to provide a method for producing such a polymer liquid crystal, a diene compound as a monomer used in the production thereof, and a method for producing the same.

Disclosure of the Invention As a result of extensive research to solve the above-mentioned problems, the present inventors discovered that a novel copolymer having, as repeating units, a chain hydrocarbon skeleton having an aromatic ring in the side chain and a siloxane skeleton exhibits the SmC ^* phase over a wide temperature range, including room temperature, and also has high-speed response to changes in electric field. Based on this finding, the present invention was completed.

That is, the present invention provides a repeating unit represented by the following general formula: [In the above formula [I] and formula [II], r and p are each 2 to
5, q is an integer from 0 to 3, m is an integer from 1 to 20, and R ¹ is where ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 , and ^R3 is ^R4 and ^R5 are _-CH3 or a halogen atom, and a and d are 0 to
10, and b is 0 or 1 (when ^R5 is _-CH3 , d is not 0).] and the molar ratio of [I] to [II] is approximately 1:1.

The number average molecular weight (Mn) of the liquid crystal copolymer of the present invention is preferably 1,000 to 1,000,000, more preferably 1,000 to 100,000.
It is 00.

If Mn is less than 1,000, the liquid crystal copolymer may not be easily molded into a film or coating, whereas if it exceeds 1,000,000, undesirable effects such as a longer response time may occur.

m is an integer of 1 to 20, preferably an integer of 6 to 12.

a and d each represent an integer of 0 to 10, but preferably a is 0 or 1 and b is an integer of 1 to 5.

The liquid crystal copolymer of the present invention can be prepared by, for example, reacting a diene compound represented by the following general formula: (wherein r, p, ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , a, b and d are the same as above) and a silicon compound represented by the following general formula: (wherein q is the same as defined above) in a substantially equimolar ratio in a solvent in the presence of a catalyst, to carry out a hydrosilylation reaction.

Preferred solvents for the hydrosilylation reaction of compound [III] and compound [IV] include inert aromatic hydrocarbons with a boiling point of 70°C or higher, such as benzene, toluene, and xylene, and inert ether solvents with a boiling point of 70°C or higher, such as tetrahydrofuran and diisopropyl ether. Preferred catalysts include platinum-based catalysts such as chloroplatinic acid (e.g., hexachloroplatinic acid hexahydrate) and dicyclopentadienylplatinum chloride. The reaction is preferably carried out in an inert atmosphere at 60 to 90°C for 5 to 20 hours.

The raw material for producing the copolymer is represented by the general formula The diene compound represented by the formula (I) is a novel compound, and the presence of repeating units derived from this raw material reduces the viscosity of the copolymer, thereby increasing the response speed to changes in electric field. This compound can be used not only for the liquid crystalline copolymer of the present invention, but also as a modifier for other liquid crystalline polymers.

Compound [III] can be, for example, a compound represented by the general formula (wherein r and p are integers of 2 to 5) and an alcohol [V] represented by the general formula X(CH ₂ ) _m X (wherein m is an integer of 1 to 20, X is -Br, -I is or The reaction mixture is purified to obtain a product, and the product is then etherified with a hydroxy compound [VII] represented by the general formula HO-R ¹ (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , a, b, and d are the same as defined above) in a solvent in the presence of an alkaline reagent.

The reaction proceeds, for example, as follows:

The alcohol [V] and the bifunctional compound [VI] are subjected to an etherification reaction in a solvent in the presence of an alkaline reagent to obtain (1), and then (1) is subjected to an etherification reaction with a hydroxy compound [VII] in a solvent in the presence of an alkaline reagent to obtain the target diene compound [III].

Specific examples of the alcohol [V] include 1,4-pentadiene-3-ol, 1,5-hexadiene-3-ol, 1,6-heptadiene-3-ol, 1,7-octadiene-3-ol, 1,6-heptadiene-4-ol,
1,7-octadien-4-ol, 1,8-nonadiene-5
-ol, 1,10-undecadien-6-ol, and the like.

Specific examples of the bifunctional compound [VI] include dibromomethane, diiodomethane, ditosylmethane, dibromoethane, diiodoethane, ditosylethane, dibromopropane, diiodopropane, ditosylpropane, dibromobutane, diiodobutane, ditosylbutane, dibromopentane, diiodopentane, ditosylpentane, dibromohexane, diiodohexane, ditosylhexane,
Dibromoheptane, diiodoheptane, ditosylheptane, dibromooctane, diiodooctane, ditosyloctane, dibromononane, diiodononane, ditosylnonane, dibromodecane, diiododecane, ditosyldecane, dibromoundecane, diiodoundecane, ditosylundecane, dibromododecane, diiodododecane,
Ditosyldodecane, dibromotridecane, diiodotridecane, ditosyltridecane, dibromotetradecane,
Examples thereof include diiodotetradecane, ditosyltetradecane, dibromopentadecane, diiodopentadecane, ditosylpentadecane, dibromohexadecane, diiodohexadecane, ditosylhexadecane, dibromoheptadecane, diiodoheptadecane, ditosylheptadecane, dibromooctadecane, diiodooctadecane, ditosyloctadecane, dibromononadecane, diiodononadecane, ditosylnonadecane, dibromoeicosane, diiodoeicosane, and ditosyleicosane.

R ¹ -OH [VII] is A compound represented by the following formula is preferably used.

Here, ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 , and ^R3 is the optically active group described above.

The optically active group in ^R2 is an optically active alcohol ^R3 -OH;
Using the optically active carboxylic acid R ³ COOH, the following reaction can be used:
It is introduced into ^R2 .

−COOH + ^R3OH → ^−COOR3 -OH + ^R3COOH → ^-OCOR3 The optically active alcohol R3 ^- OH used here is
(+)-2-Methylbutanol, (-)-2-Methylbutanol, (+)-2-Chlorobutanol, (-)-2
-Chlorbutanol, (+)-2-methylpentanol, (-)-2-methylpentanol, (+)-3-methylpentanol, (-)-3-methylpentanol,
(+)-4-methylhexanol, (-)-4-methylhexanol, (+)-2-chloropropanol,
(-)-2-chloropropanol, (+)-6-methyloctanol, (-)-6-methyloctanol,
(+)-2-cyanobutanol, (-)-2-cyanobutanol, (+)-2-butanol, (-)-2-butanol, (+)-2-pentanol, (-)-2-pentanol, (+)-2-octanol, (-)-2-octanol, (+)-1,1,1-trifluoro-2-octanol, (-)-1,1,1-trifluoro-2-octanol, (+)-2-fluorooctanol, (-)-
2-Fluorooctanol, (+)-2-fluoroheptanol, (-)-2-fluoroheptanol, (+)
-2-fluorohexanol, (-)-2-fluorohexanol, (+)-2-fluorononanol, (-)
-2-fluorononanol, (+)-2-chloro-3-
methylpentanol, (-)-2-chloro-3-methylpentanol, and the like.

Here, examples of the optically active carboxylic acid R ³ —COOH include (+)-2-methylbutanoic acid, (−)-2-methylbutanoic acid, (+)-2-chlorobutanoic acid, (−)-2-chlorobutanoic acid, (+)-2-methylpentanoic acid, (−)
-2-methylpentanoic acid, (+)-3-methylpentanoic acid, (-)-3-methylpentanoic acid, (+)-4-methylhexanoic acid, (-)-4-methylhexanoic acid, (+)
-2-chloropropanoic acid, (-)-2-chloropropanoic acid, (+)-6-methyloctanoic acid, (-)-6-methyloctanoic acid, (+)-2-cyanobutanoic acid, (-)-
2-Cyanobutanoic acid, (+)-2-fluorooctanoic acid, (-)-2-fluorooctanoic acid, (+)-2-chloro-3-methylpentanoic acid, (-)-2-chloro-3
-methylpentanoic acid, etc.

Among the alcohols [VII] represented by R ¹ -OH, pyrimidine derivatives are novel compounds, and their preparation methods are shown below.

Hydrogen chloride gas is blown into 4-hexoxybenzonitrile in an ethanol solvent, and the solvent is concentrated to give (a). Next, (a) is dissolved in methanol, and ammonia gas is blown in to cause a reaction, followed by concentration to give amidine salt (b).

The amidine salt (b), 2-ethoxycarbonyl-3
- dimethylaminoacrolein in an ethanol solvent,
Sodium ethoxide is added and reacted to give the compound (c).
get.

(c) is deprotected by treatment with HBr/acetic acid to give (d), which is then acetylated with acetic anhydride to give (e).

The acetylated carboxylic acid derivative (e) is converted to an acid chloride (f) using thionyl chloride or the like, and then esterified with an optically active alcohol to give an ester such as (g). The acetyl protecting group is then removed using benzylamine or the like to give the desired alcohol.

The same procedure is carried out using 4-methoxy-4'-cyanobiphenyl instead of the 4-methoxybenzonitrile used in the preparation of (1), to give the desired product.

Butyllithium was added to a THF solution of methoxymethyltriphenylphosphonium bromide, and then methyl 4
-Formyl benzoate is added and reacted to give (h).

Phosphorus oxychloride is added to a DMF solvent, and the above benzoate compound is added, followed by pouring into an aqueous sodium perchlorate solution to obtain iminium salt (i).

the iminium salt (i), The amidine salt (b) obtained in the manufacturing process of (1) is reacted with sodium methoxide in a methanol solvent to obtain (j).

below Similar to the preparation of (I), deprotection (k), acetylation (1),
The target compound is obtained by carrying out acid chloride conversion (m), esterification (n) and deprotection.

BrCH ₂ CH(OC ₂ H ₅ ) ₂ + HOR ³ → (C ₂ H ₅ O) ₂ CHCH ₂ -OR ³ (o) An optically active alcohol is dissolved in THF and reacted with sodium hydride, then reacted with bromoacetaldehyde diethyl acetal to obtain (o).

Phosphorus oxychloride was added to N,N-dimethylformamide, and then (o) was added and reacted to obtain (p).

Hydrogen chloride gas is bubbled into an ethanol solution of 4-benzyloxybenzonitrile, and the solution is concentrated. The solution is then dissolved in methanol, and ammonia gas is bubbled into the solution to obtain (q).

Sodium methoxide is added to an ethanol solvent of (p) and (q) to react to obtain (r). Next, (r) is deprotected using a palladium carbon catalyst in a hydrogen gas atmosphere to obtain the target compound.

The target compound can be obtained by the same procedure as in the preparation of (1), except that 4'-benzyloxy-4-cyanobiphenyl is used in place of 4-benzyloxybenzonitrile.

4-Hydroxybenzaldehyde, optically active p-toluenesulfonate, and potassium carbonate are reacted in an acetone solution to obtain the ether (s).

Butyllithium is added to a THF solution of methoxymethyltriphenylphosphonium bromide.
Adding and reacting gives (t).

Phosphorus oxychloride was added to a DMF solvent, and then (t) was added, followed by pouring into an aqueous sodium perchlorate solution to obtain an iminium salt (u).

The iminium salt (u), The amidine salt (q) obtained in the manufacturing process of (1) is reacted with sodium methoxide in a methanol solvent to obtain (v).

Next, (v) is subjected to deprotection using a palladium carbon catalyst in a hydrogen gas atmosphere to obtain the target compound.

As the solvent for the etherification reaction, for example, an aprotic polar solvent such as tetrahydrofuran or N,N-dimethylformamide is preferably used, and as the etherification reaction reagent, for example, a metal hydride such as sodium hydride, a metal hydroxide such as potassium hydroxide or sodium hydroxide, or -
A basic compound capable of ionizing OH is preferably used.

The etherification reaction is carried out by introducing an alkaline reagent into a mixture of the alcohol [V] and a solvent to form an alkoxide at room temperature.
(However, in the case of compounds or reagents with low reactivity, heating is required.) Next, the dibromo compound [VI] is introduced and the temperature is raised to 60-100°C.
The mixture is heated and stirred at RT.

Suitable solvents for the etherification reaction include ketone solvents such as acetone and methyl ethyl ketone, inert ether solvents such as tetrahydrofuran and ether, and lower alcohols such as methanol and ethanol. Suitable etherification reaction reagents include carbonates such as potassium carbonate and sodium carbonate, potassium hydroxide,
Metal hydroxides such as sodium hydroxide are preferably used.

The etherification reaction is carried out by introducing the hydroxy compound [VII], the dibromo compound [VI], an alkaline reagent and a solvent in any order, and heating and stirring at 60 to 100°C.

In addition to the above-mentioned methods, compound [III] can be obtained by, for example, the method represented by the general formula (wherein r and p are integers of 2 to 5) and an alcohol [V] represented by the general formula X(CH ₂ ) _m X (wherein m is an integer of 1 to 20, and X is -Br, -I, or The bifunctional compound [VI] represented by the general formula is subjected to an etherification reaction in a solvent in the presence of an alkaline reagent, and the product obtained by purifying the resulting reaction mixture is mixed with a compound represented by the general formula (wherein e is 1 or 2) in a solvent in the presence of an alkaline reagent, and the resulting reaction mixture is filtered to obtain a product, which is then hydrolyzed in an alkali, water, or alcohol. The resulting reaction mixture is poured into water, and a mineral acid is added to make the pH acidic. The resulting solution is then extracted with ether. The ether is removed and the resulting solid is reacted with an acid halogenating agent to obtain an acid chloride, which is then reacted with a compound [VIII] represented by the general formula HO-AR ² (wherein A is The compound can be produced by esterifying a hydroxy compound [IX] represented by the formula (I) in a solvent.

The reaction proceeds, for example, as follows:

Hydroxy compounds used in esterification reactions [I
X] as The optically active group ^R2 is introduced in the same manner as described above.

The production of compound (1) by etherification reaction is the same as described above.

Next, compound (1) and the general formula The compound (VIII) represented by the following formula (1) is subjected to an etherification reaction in a solvent in the presence of an alkaline reagent to obtain a compound (3).

Next, the compound (4) is hydrolyzed by heating in an alkali, water or alcohol as necessary, and then halogenated using an acid halogenating agent to form an acid chloride. Then, the compound (4) is esterified with a hydroxy compound (IX) represented by the general formula HO- ^AR2 using triethylamine, a THF solvent or the like to obtain the target diene compound (5), i.e., diene compound (III).

Specific examples of the compound [VIII] include methyl 4-hydroxybenzoate and methyl 4'-hydroxybiphenyl-4-carboxylate.

The solvent, reagents, and reaction conditions in the etherification reaction are the same as those in the etherification reaction.

In the hydrolysis, metal hydroxides such as potassium hydroxide and sodium hydroxide are preferably used as the alkali, and water-soluble lower alcohols such as methanol and ethanol are preferably used as the alcohol. The hydrolysis reaction may be carried out by heating only the ester compound, the alkali catalyst, and water, but if an alcohol is further added, the solubility of the ester compound as a raw material is improved and the reaction proceeds more easily.

For the halogenation reaction, a known acid halogenating agent such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, etc. is used.

Suitable solvents for the esterification reaction include, for example, inert ether solvents such as tetrahydrofuran and inert hydrocarbon solvents such as toluene and hexane.

The esterification reaction is carried out by introducing the acid chloride or the acid chloride dissolved in a solvent into a solution of a hydrogen halide acceptor such as pyridine and a tertiary amine such as triethylamine, and stirring the mixture.

If the reactivity is low, the reaction may be heated to 20 to 80°C.

Next, two Si-
Silicon compounds with H-bonds [IV] include 1,1,3,
3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, and the like.

In this manner, the liquid crystal copolymer of the present invention and the diene compound used in the production thereof are obtained.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 to 16 are IR charts of the copolymers obtained in Examples 1 to 16, respectively.

17 and 18 are ¹ H-NMR charts of the copolymers obtained in Examples 17 and 18, respectively.

FIG. 19 shows ^{the 1H} -NM of the diene compound obtained in Example 19.
This is an R chart.

FIG. 20 is a ¹ H-NMR chart of the copolymer obtained in Example 19.

FIG. 21 is a ¹ H-NMR chart of the copolymer obtained in Example 20.

FIG. 22 is a ¹ H-NMR chart of the copolymer obtained in Example 21.

FIG. 23 shows ^{the 1H} -NM of the diene compound obtained in Example 22.
This is an R chart.

FIG. 24 is a ¹ H-NMR chart of the copolymer obtained in Example 22.

FIG. 25 shows ^{the 1H} -NM of the diene compound obtained in Example 23.
This is an R chart.

FIG. 26 is a ¹ H-NMR chart of the copolymer obtained in Example 23.

FIG. 27 is a ¹ H-NMR chart of the copolymer obtained in Example 24.

FIG. 28 shows ^{the 1H} -NM of the diene compound obtained in Example 25.
This is an R chart.

FIG. 29 is a ¹ H-NMR chart of the copolymer obtained in Example 25.

BEST MODE FOR CARRYING OUT THE INVENTION In the following examples, the electric field response speed was measured as follows.

Examples 1 to 18 A liquid crystal material was sandwiched between two 20 x 10 mm ITO substrates, the thickness of which was adjusted to 2.5 µm using spacers, and an AC electric field E = 2 x 10 ⁶
A voltage of V/m was applied, and the response time of the change in the amount of transmitted light (0 to 90%) was measured.

Examples 19 to 25: A liquid crystal material was sandwiched between two circular ITO-coated glass substrates with an electrode area of 0.2 ^cm2 , the thickness was adjusted to 1 to 2 μm using spacers, and shear stress was applied 3 to 5 times to orient the liquid crystal. The resulting liquid crystal optical element was sandwiched between two polarizing plates with orthogonal polarization axes to prepare a liquid crystal cell. A ±10 MV/M square wave was then applied to this liquid crystal cell, and the time ( _t10-90 ) required for the amount of transmitted light to change (10% to 90%) was measured and used as the electric field response time.

In the formula showing the phase transition behavior, each symbol has the following meaning.

Cry: Crystal, SmC ^* : Chiral smectic C liquid crystal phase, Sm
A: Smectic A liquid crystal phase, Iso: Isotropic liquid, Sml: Unidentified smectic liquid crystal phase, N ^* : Chiral nematic liquid crystal phase Example 1 0.1 mol of 4-hydroxybenzoic acid, 0.3 mol of optically active 2-methylbutanol, and 0.1 ml of concentrated sulfuric acid were refluxed in 1 liter of toluene to carry out a dehydration reaction. The reaction solution was concentrated and purified by column chromatography to obtain the desired ester (1) (yield 97%). 0.1 mol of 1,5-hexadien-3-ol and 0.17 mol of sodium hydride were stirred in 150 ml of THF at room temperature for 1 hour. 0.3 mol of 1,6-diiodohexane was then added to the reaction system and refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (2) (yield: 67%). 60 mmol of the ether (2) obtained in [2], 4'
- 150 ml of acetone with 60 mmol of hydroxybiphenyl-4-carboxylic acid methyl ester and 0.2 mol of potassium carbonate
The solution was refluxed for 12 hours, and the reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (3) (yield: 66%). A solution of 30 mmol of the ether (3) obtained in [3], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water is refluxed for 30 minutes. The resulting reaction solution is poured into 500 ml of water, and the pH is adjusted to 2 with dilute HCl water. The reaction solution is extracted with ether.
After drying and concentration, the mixture was purified by column chromatography.
The desired carboxylic acid derivative (4) was obtained (yield 98%).
%) 20 mmol of the carboxylic acid derivative (4) obtained in [4] was dissolved in 30 ml of thionyl chloride and 20 ml of toluene solution, and 0.1 ml of pyridine.
1 was introduced and stirred at room temperature for 3 hours. The reaction mixture was distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride. 25 mmol of the ester (1) obtained in [1] and 30 mmol of triethylamine were dissolved in 80 ml of THF and stirred at room temperature. Next, 30 ml of the acid chloride solution obtained earlier was added dropwise to the solution and stirred for 12 hours. The reaction mixture was extracted with ether, dried, and concentrated, and then purified by column chromatography to obtain the desired diene compound (5). (Yield: 59%) This diene compound exhibited liquid crystallinity and showed the following phase transition behavior and physical properties. The elemental analysis results were also analyzed by a second
As shown in the table.

Response time: 42 μs (77°C), 115 μs (57°C), 390 μs
(37°C) Tilt angle (2θ): 61° (30°C) -Polyaddition reaction- and a copolymer bonded in a 1:1 ratio. [5] 10 mmol of the diene compound (5), 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (88% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 1.

Example 2 0.1 mol of 1,5-hexadien-3-ol and 0.17 mol of sodium hydride were stirred in 150 ml of THF at room temperature for 1 hour. 0.3 mol of 1,8-ditosyl octane was then added to the reaction system and refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (6) (yield: 69%). 60 mmol of the ether (6) obtained in [1], 4'
- 150 ml of acetone with 60 mmol of hydroxybiphenyl-4-carboxylic acid methyl ester and 0.2 mol of potassium carbonate
The solution was refluxed for 12 hours, filtered, concentrated, and purified by column chromatography to obtain the desired ether (7) (yield: 67%). A solution of 30 mmol of the ether (7) obtained in [2], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water is refluxed for 30 minutes. The reaction mixture is poured into 500 ml of water and diluted with HCl.
The pH was adjusted to 2 with water, and the reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (8) (yield: 98%). 20 mmol of the carboxylic acid derivative (8) obtained in [3] was dissolved in 30 ml of thionyl chloride in 20 ml of toluene and 0.1 ml of pyridine.
The reaction mixture is then distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride.
The solution was stirred at room temperature. Next, a 30 ml solution of the acid chloride obtained earlier in THF was added dropwise, and the mixture was stirred for 12 hours. The reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired diene compound (9).
This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties: The results of elemental analysis are shown in Table 2.

Response time: 13 μs (55°C), 41 μs (35°C), 300 μs
(15°C) Tilt angle (2θ): 76° (25°C) -Polyaddition reaction- and a copolymer bonded in a 1:1 ratio. 10 mmol of the diene compound (9) obtained in [4], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to yield the desired copolymer (78% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 2.

Example 3 Hydroquinone 0.3 mol, optically active 2-fluorooctanol tosylate 0.2 mol, and potassium hydroxide 0.4
The resulting mixture was refluxed in 1 liter of methyl ethyl ketone under an argon atmosphere for 12 hours. The reaction mixture was concentrated and purified by column chromatography to obtain the desired phenol (10) (yield: 57%). 0.1 mol of 1,5-hexadiene-3-ol and 0.17 mol of sodium hydride were stirred in 150 ml of THF at room temperature for 1 hour. 0.3 mol of 1,10-dibromodecane was then added and refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (11) (yield: 63%). 60 mmol of the ether (11) obtained in [2], 4'
- 150 ml of acetone with 60 mmol of hydroxybiphenyl-4-carboxylic acid methyl ester and 0.2 mol of potassium carbonate
The solution was refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (12) (yield: 62%). A solution of 30 mmol of the ether (12) obtained in [3], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water is refluxed for 30 minutes. The reaction mixture is poured into 500 ml of water and diluted with HCl.
The pH was adjusted to 2 with water, and the reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (13) (yield 95%). 20 mmol of the carboxylic acid derivative (13) obtained in [4] was dissolved in 30 ml of thionyl chloride and 20 ml of toluene solution in 0.1 ml of pyridine.
1 was introduced and stirred at room temperature for 3 hours. The reaction mixture was distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride. A solution of 25 mmol of the phenol (10) obtained in [1] and 30 mmol of triethylamine in 80 ml of THF was stirred at room temperature. Next, a solution of the acid chloride obtained previously in 30 ml of THF was added dropwise, and the mixture was stirred for 12 hours. The reaction mixture was extracted with ether,
After drying and concentration, the mixture was purified by column chromatography to obtain the target diene compound (14). (Yield: 59%) This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. In addition, the elemental analysis results were confirmed by a second analysis.
As shown in the table.

Response time: 9 μs (121°C), 13 μs (101°C), Tilt angle: 72° (100°C) -Polyaddition reaction- 10 mmol of the diene compound (14) obtained in [5], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (78% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 3.

Example 4 0.1 mol of 1,5-hexadien-3-ol and 0.17 mol of sodium hydride are stirred in 150 ml of THF at room temperature for 1 hour. Then, 0.3 mol of 1,12-dibromododecane is introduced.
The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (15) (yield: 55%). 60 mmol of the ether (15) obtained in [1], 4-
A solution of 60 mmol of hydroxybenzoic acid methyl ester and 0.2 mol of potassium carbonate in 150 ml of acetone was refluxed for 12 hours. The reaction mixture was filtered, concentrated, and then purified by column chromatography to obtain the desired ether (16). (Yield:
77%) A solution of 30 mmol of the ether (16) obtained in [2], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water was
The reaction mixture was poured into 500 ml of water, and the pH was adjusted to 2 with diluted HCl water. The reaction mixture was extracted with ether, dried, and concentrated.
Purification by column chromatography gave the desired carboxylic acid derivative (17) (yield 96%). 20 mmol of the carboxylic acid derivative (17) obtained in [3] was dissolved in 20 ml of toluene (30 ml) and 0.1 ml of pyridine.
The reaction mixture is then distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride.
A solution of 25 mmol of methylbutyl ester and 30 mmol of triethylamine in 80 ml of THF is stirred at room temperature.
A 30 ml solution of the acid chloride obtained above in THF was added dropwise, and the mixture was stirred for 12 hours. The reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the target diene compound (18). (Yield: 63%) This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The elemental analysis results were also confirmed by a second analysis.
As shown in the table.

Response time: 19 μs (59°C), 38 μs (39°C), 310 μs
(19°C) Tilt angle (2θ): 69° (40°C) -Polyaddition reaction- 10 mmol of the diene compound (18) obtained in [4], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (conversion rate: 69%). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum is shown in Figure 4.

Example 5 Hydroquinone 0.3 mol, optically active 2-chloro-3
0.1 mol of 1-methylpentanoic acid and 0.1 mg of concentrated sulfuric acid were refluxed in 1 L of toluene to carry out a dehydration reaction. The reaction solution was concentrated and purified by column chromatography to obtain the desired ester (20) (yield 56%). A solution of 60 mmol of the ether (11) obtained in Example 3-[2], 60 mmol of methyl 4-hydroxybenzoate, and 0.2 mol of potassium carbonate in 150 ml of acetone was refluxed for 12 hours. The reaction mixture was filtered and concentrated, and then purified by column chromatography to obtain the desired ether (21) (yield 77%). A solution of 30 mmol of the ether (21) obtained in [2], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water was refluxed for 30 minutes. The reaction mixture was poured into 500 ml of water, and the pH was adjusted to 2 with dilute aqueous HCl. The reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (22) (yield 96%). 20 mmol of the carboxylic acid derivative (22) obtained in [3] was dissolved in 30 ml of thionyl chloride and 20 ml of toluene solution in 0.1 ml of pyridine.
1 was introduced and stirred at room temperature for 3 hours. The reaction mixture was distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride. A solution of 25 mmol of the ester (20) obtained in [1] and 30 mmol of triethylamine in 80 ml of THF was stirred at room temperature. Next, a 30 ml THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 12 hours. The reaction mixture was extracted with ether, dried, and concentrated, and then purified by column chromatography to obtain the desired diene compound (23). (Yield: 44%) This diene compound exhibited liquid crystallinity and showed the following phase transition behavior and physical properties. The elemental analysis results were also analyzed by a second
As shown in the table.

Response time: 230 μs (-16°C) Tilt angle (2θ): 41° (-16°C) -Polyaddition reaction- Copolymer with.

10 mmol of the diene compound (23) obtained in [5], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (88% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum is shown in Figure 5.

Example 6 0.1 mol of 1,5-hexadiene-3-ol and 0.17 mol of sodium hydride were stirred in 150 ml of THF at room temperature for 1 hour. 0.3 mol of 1,9-dibromononane was then added and refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (24).
(Yield 55%) 60 mmol of the ether (24) obtained in [1], 4'
A solution of 60 mmol of 1-methylheptyl-4-hydroxybiphenyl-4-carboxylic acid ester and 0.2 mol of potassium carbonate in 150 ml of acetone was refluxed for 12 hours. The reaction mixture was filtered.
After concentration, the mixture was purified by column chromatography to obtain the target diene compound (25). (Yield: 72%) This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 88 μs (31°C) Tilt angle (2θ): 49° (31°C) −Polyaddition reaction− 10 mmol of the diene compound (25) obtained in [2], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (71% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 6.

Example 7 A solution of 60 mmol of the ether (15) obtained in Example 4-[1], 60 mmol of methyl 4-hydroxybiphenyl-4-carboxylate, and 0.2 mol of potassium carbonate in 150 ml of acetone was refluxed for 12 hours. The reaction mixture was filtered and concentrated, and then purified by column chromatography to obtain the desired ether (26) (yield: 69%). A solution of 30 mmol of the ether (26) obtained in [1], 0.1 mol of sodium hydroxide, 50 ml of ethanol, and 20 ml of water is refluxed for 30 minutes. The reaction mixture is poured into 500 ml of water and diluted with HCl.
The pH was adjusted to 2 with water, and the reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (27) (yield 96%). 20 mmol of the carboxylic acid derivative (27) obtained in [2] was dissolved in 30 ml of thionyl chloride and 20 ml of toluene solution in 0.1 ml of pyridine.
The reaction mixture is then distilled under reduced pressure to remove the solvent and excess thionyl chloride, yielding the acid chloride.
The solution was stirred at room temperature. Next, a 30 ml solution of the acid chloride obtained earlier in THF was added dropwise, and the mixture was stirred for 12 hours. The reaction mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain the desired diene compound (28). (Yield: 69%) This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The elemental analysis results were also confirmed by a second analysis.
As shown in the table.

Response time: 98 μs (31°C), 529 μs (11°C) Tilt angle (2θ): 53° (31°C) −Polyaddition reaction− 10 mmol of the diene compound (28) obtained in [3], 1,
A toluene solution of 10 mmol of 1,3,3,5,5-hexamethyltrisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction solution was concentrated and then purified by column chromatography to yield the desired copolymer (74% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 7.

Example 8 0.1 mol of 1,6-heptadien-4-ol and 0.17 mol of sodium hydride were stirred in 150 ml of THF at room temperature for 1 hour. 0.3 mol of 1,10-dibromodecane was then added and refluxed for 12 hours. The reaction mixture was filtered, concentrated, and purified by column chromatography to obtain the desired ether (29) (yield: 61%). Synthesis of compound (30) 40 g of 4-hydroxybenzaldehyde, (S)-1-
80 g of methylbutyl p-toluenesulfonate and 46 g of potassium carbonate were refluxed in acetone for 12 hours, and the insoluble matter was removed from the reaction mixture while it was still hot. The solvent was then distilled off, and the residue was purified by column chromatography to give 4-(1-methylbutyloxy)benzaldehyde (30).

Synthesis of Compound (31) 120 g of methoxymethyltriphenylphosphonium bromide in tetrahydrofuran (THF) under an argon atmosphere
Butyllithium hexane solution was added to the solution, and the mixture was stirred at room temperature for 1
The mixture was stirred for 1 hour. Compound (30) was added as a THF solution. Stirring was continued for 2 hours. The reaction mixture was washed with water, and then diluted with sulfuric acid and
The mixture was dried over magnesium and concentrated. The residue was purified by column chromatography to give 1-(2-methoxyethenyl)-4-(1-methylbutyloxy)benzene (3
1) was obtained.

Synthesis of Compound (32): 100 ml of N,N-dimethylformamide (DMF) was cooled to 0°C. 75 g of phosphorus oxychloride was added dropwise. The mixture was stirred at room temperature for 30 minutes. Compound (31) was added as a DMF solution. The mixture was stirred at 50°C for 1 hour. After cooling, the mixture was poured into an aqueous sodium perchlorate solution, and the resulting iminium salt crystals (32) were collected and dried for use in the subsequent reaction.

Synthesis of Compound (33) 50 g of 4-benzyloxybenzonitrile was dissolved in dry ethanol and cooled. Hydrogen chloride gas was blown into the solution, and the mixture was stirred at room temperature for 2 days. The reaction solution was concentrated under reduced pressure, and then
The product was dissolved in methanol, and ammonia gas was blown into the solution, followed by stirring for one day. The solvent was removed from the reaction mixture by distillation under reduced pressure to obtain amidine salt (33).

Synthesis of Compound (34) Compound (32) and 41 g of the amidine salt (33) obtained in [5] were dissolved in methanol. 8.5 g of sodium methoxide was added and refluxed for 2 hours. Insoluble materials were removed from the reaction solution while it was still hot, and the solution was concentrated. The concentrated solution was dissolved in ethyl acetate and hydrogenated using palladium carbon as a catalyst. The reaction solution was concentrated, and the residue was recrystallized from a mixed solvent of hexane and toluene.
The phenolic compound (34) was obtained.

Yield: 28.5 g (26% yield from 4-benzyloxybenzaldehyde) 30 mmol of the ether (29) obtained in [1],
A solution of 30 mmol of the phenol (34) obtained in [6] and 0.1 mol of potassium carbonate in 100 ml of acetone was refluxed for 12 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the target diene compound (35).
(Yield: 49%) This diene compound exhibits liquid crystallinity and the following phase transition behavior: The results of elemental analysis are shown in Table 2.

Response time: 25 μs (41°C), 109 μs (21°C), 143 ms
(1°C) Tilt angle (2θ): 60° (21°C) -Polyaddition reaction- 10 mmol of the diene compound (35) obtained in [7], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (72% conversion). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 8.

0.1 mol of 4-acetoxybenzoic acid to 70 ml of thionyl chloride
The mixture was then stirred at 80°C for 3 hours. The reaction mixture was distilled under reduced pressure to remove excess thionyl chloride and obtain the acid chloride. A 500ml solution of optically active 2-fluoroheptanol (0.1 mol) and triethylamine (0.12 mol) in THF was stirred, to which the THF solution of the acid chloride obtained earlier was added dropwise, followed by stirring for 12 hours. The reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the desired ester (36) (yield 77%). A solution of 70 mmol of the ester (36) obtained in [1] and 50 ml of benzylamine in 300 ml of ether was stirred for 1 hour. The reaction mixture was washed with water, dried, concentrated, and then purified by column chromatography to obtain the desired phenol (37) (yield 95%). Carboxylic acid derivative (22) obtained in Example 5-[3]
20 ml of thionyl chloride was added to 50 moles of the phenol (37) and stirred at 80°C for 3 hours. The reaction mixture was distilled under reduced pressure to remove excess thionyl chloride, yielding an acid oxide. Next, 50 mmol of the phenol (37) obtained in [2] and 60 mmol of triethylamine were added.
The 150 ml THF solution was stirred, and the THF solution of the acid chloride obtained above was added dropwise, followed by stirring for 12 hours. The reaction solution was extracted with ether,
After drying and concentration, the mixture was purified by column chromatography.
The target diene compound (38) was obtained (yield: 63%). This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 112 μs (30°C) Tilt angle (2θ): 50° (30°C) −Polyaddition reaction− 10 mmol of the diene compound (38) obtained in [7], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to yield the desired polymer (88% conversion). The molecular weight, phase transition temperature, and response time of the resulting polymer are shown in Table 1, and its IR spectrum is shown in Figure 9.

Example 10 Synthesis of Compound (39) 40 g of 4-methoxybenzonitrile was dissolved in ethanol and cooled. Dry hydrogen chloride gas was blown into the solution.
The reaction mixture was stirred at room temperature for 2 days. After concentrating the reaction mixture under reduced pressure, the mixture was dissolved in methanol, and ammonia gas was blown into the mixture, followed by stirring for 1 day. The solvent was removed from the reaction mixture under reduced pressure to obtain the amidine salt (39).

Synthesis of Compound (40) The above amidine salt (39), 2-ethoxycarbonyl-3
- 50 g of dimethylaminoacrolein is mixed in ethanol, and 45 g of sodium ethoxide is added little by little.
The mixture was refluxed for 2 hours, and insoluble materials were removed from the reaction mixture by filtration while it was still hot. The mixture was then allowed to cool, and the resulting precipitate (40) was collected.

Synthesis of Compound (41) After deprotecting (40) obtained in [2] by treatment with HBr/acetic acid, the compound was acetylated by heating and stirring in acetic anhydride at 120°C for 1 hour to obtain (41).

Synthesis of Compound (42) After drying under reduced pressure, (41) obtained in [3] was refluxed in thionyl chloride and concentrated to give an acid chloride.

The acid chloride was dissolved in toluene, and (S)
A toluene solution containing 15 g of 2-pentanol and 20 g of pyridine was added dropwise. The mixture was stirred at room temperature for one day. Insoluble matter was removed from the reaction mixture by filtration and concentrated under reduced pressure. The residue was dissolved in ether, and 35 g of benzylamine was added. The mixture was stirred at room temperature for three hours. The reaction mixture was washed with dilute hydrochloric acid, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain the phenol (42).

Yield: 28.3 g (33% yield from 4-methoxybenzonitrile)
%) A solution of 30 mmol of the ether (11) obtained in Example 3-[2], 30 mmol of the phenol (42) obtained in [4], and 0.1 mol of potassium carbonate in 150 mL of acetone was refluxed for 12 hours. The reaction mixture was filtered and concentrated, and then purified by column chromatography to obtain the desired diene compound (43) (yield: 39%). This diene compound exhibited liquid crystallinity and the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 210 μs (21°C) Tilt angle (2θ): 56° (21°C) −Polyaddition reaction− 10 mmol of the diene compound (43) obtained in [5], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and purified by column chromatography to obtain the desired copolymer (yield 62%). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum is shown in Figure 10.

Example 11 Carboxylic acid derivative (17) obtained in Example 4-[3]
20 ml of thionyl chloride was added to 50 mmol of the reaction mixture and stirred at 80°C for 3 hours. Excess thionyl chloride was removed by vacuum distillation to obtain the acid chloride. Next, 50 mmol of the phenol (42) obtained in Example 10-[4] and triethylamine were added to the reaction mixture.
Add 60 ml of the 150 ml THF solution to the acid chloride obtained above and stir.
The THF solution was added dropwise and stirred for 12 hours. The reaction mixture was extracted with ether, dried, concentrated, and then purified by column chromatography to obtain the target diene compound (44). (Yield: 41
%) This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 106 μs (32°C) Tilt angle (2θ): 43° (32°C) −Polyaddition reaction− 10 mmol of the diene compound (44) obtained in [1], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (yield: 52%). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum is shown in Figure 11.

Example 12 Synthesis of compound (45) 120 g of methoxymethyltriphenylphosphonium bromide in tetrahydrofuran (THF) under an argon atmosphere
The butyllithium-hexane solution was added to the solution and stirred at room temperature for 1 hour. 50 g of methyl 4-formylbenzoate was added as a THF solution and stirred for 2 hours. The reaction mixture was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 47 g of methyl 4-(2-methoxyethenyl)benzoate (45).

Synthesis of Iminium Salt (46) 100 ml of dimethylformamide (DMF) was cooled to 0°C, and 40 g of phosphorus oxychloride was added dropwise. The mixture was returned to room temperature and stirred for 30 minutes. The above benzoate (45) was added as a DMF solution, and the mixture was stirred at 50°C for 1 hour. After cooling, the mixture was poured into an aqueous sodium perchlorate solution, and the resulting iminium salt (46) was obtained.
The crystals were collected, dried and used in the next reaction.

Synthesis of Compound (47) The above iminium salt (46) and 42 g of the amidine salt (39) obtained in Example 10-[1] were dissolved in methanol, and 25 g of sodium methoxide was added little by little. The mixture was refluxed for 2 hours. Insoluble matter was removed from the reaction mixture while it was still hot, and the mixture was allowed to cool. The resulting precipitate (4
7) were collected.

Synthesis of acetylated derivative (48) After deprotecting (47) by HBr/acetic acid treatment, the acetylated derivative (48) was obtained by heating and stirring in acetic anhydride at 120°C for 1 hour.
8) was obtained.

Synthesis of Compound (51) The acetyl compound (48) was dried under reduced pressure and then refluxed in thionyl chloride to give the acid chloride compound (49).

The acid chloride and toluene derivatives were dissolved in toluene, and a toluene solution containing 15 g of (S)-2-pentanol and 20 g of pyridine was added dropwise to the solution. After stirring at room temperature for one day, insoluble matter was removed from the reaction solution by filtration and concentrated under reduced pressure. The residue was dissolved in ether, and 35 g of benzylamine was added and stirred at room temperature for 3 hours. The reaction solution was washed with dilute hydrochloric acid, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain the phenol derivative (51).
obtained.

Yield: 33 g (30% yield from methyl 4-formylbenzoate) A solution of 30 mmol of the ether (11) obtained in Example 3-[2], 30 mmol of the phenol (51) obtained in [5], and 0.1 mol of potassium carbonate in 150 mL of acetone was refluxed for 12 hours. The reaction mixture was filtered and concentrated, and then purified by column chromatography to obtain the desired diene compound (52) (yield: 39%). This diene compound exhibited liquid crystallinity and the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 26 μs (87°C), 82 μs (67°C) Tilt angle (2θ): 68° (67°C) -Polyaddition reaction- 10 mmol of the diene compound (52) obtained in [6], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and then purified by column chromatography to obtain the desired copolymer (71% yield). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 12.

Example 13 30 mol of the ether compound (11) obtained in Example 3-[2], 30 mol of the phenol compound (34) obtained in Example 8-[6]
millimoles, 150 ml of acetone solution of 0.1 mol of potassium carbonate
The reaction mixture was stirred for 12 hours. After filtering and concentrating the reaction mixture, it was purified by column chromatography to obtain the target diene compound (5
3) was obtained (yield: 42%). This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are shown in Table 2.

Response time: 115 μs (59°C), 815 μs (39°C) Tilt angle (2θ): 88° (39°C) −Polyaddition reaction− 10 mmol of the diene compound (53) obtained in [1], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and purified by column chromatography to obtain the desired copolymer (yield 67%). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum is shown in Figure 13.

Example 14 Synthesis of Compound (54): 35 g of (S)-2-pentanol was dissolved in tetrahydrofuran, and 16 g of 60% sodium hydride was added. After stirring for 30 minutes, 80 g of bromoacetaldehyde diethyl acetal was added and refluxed for 6 hours. The reaction solution was concentrated, and water and ether were added and the mixture was shaken. The organic layer was collected, dried over magnesium sulfate, and the solvent was removed. Purification by column chromatography yielded 2-(4-methylbutyloxy)acetaldehyde diethyl acetal (54).

Synthesis of Compound (55) A solution of 30 g of dry N,N-dimethylformamide in dry dichloroethane was cooled to below 5°C. A dichloroethane solution containing 63 g of phosphorus oxychloride was added dropwise to this solution, and the mixture was stirred at below 5°C for 30 minutes. Compound (54) was then added to the reaction mixture.
was added dropwise as a dichloroethane solution, and the mixture was stirred at room temperature for 30 minutes, and then stirred at 70°C for 1 hour. The reaction mixture was cooled to room temperature, poured into ice water, and made alkaline by adding potassium carbonate. The reaction mixture was concentrated under reduced pressure, and then heated and stirred.
The extract was dried over magnesium sulfate, and the solvent was removed by distillation. The residue was distilled under reduced pressure to obtain 2-(1-methylbutyloxy)-3-dimethylaminoacrolein (55). (bp: 150-155°C/5mmHg) Synthesis of amidine salt (56): 70 g of 4'-benzyloxy-4-cyanobiphenyl was dissolved in dry ethanol and cooled. Hydrogen chloride gas was bubbled into the solution and stirred for one day. The reaction solution was concentrated under reduced pressure, then dissolved in methanol, ammonium gas was bubbled into the solution, and stirred for one day. The solvent was then distilled off under reduced pressure to obtain amidine salt (56).

Synthesis of Compound (58): 53 g of Compound (56) and 55 g of Compound (55) were mixed in ethanol, and 12 g of sodium methoxide was added in small portions. The reaction mixture was refluxed for 2 hours, and insoluble materials were removed while hot. The solvent was distilled off, and the residue was purified by column chromatography to obtain Compound (57). The obtained Compound (57) was dissolved in ethyl acetate and hydrogenated using palladium carbon as a catalyst. The solvent was distilled off from the reaction mixture, and the product was recrystallized from a hexane-toluene mixed solvent to obtain the target product (58).

Yield: 41 g (48% yield from 4'-benzyloxy-4-cyanobiphenyl) A solution of 30 mmol of the ether (11) obtained in Example 3-[2], 30 mmol of the phenol (58) obtained in [4], and 0.1 mol of potassium carbonate in 150 ml of acetone was stirred for 12 hours. The reaction mixture was filtered and concentrated, and then purified by column chromatography to obtain the target diene compound (59) (yield 52%). This diene compound exhibited liquid crystallinity and the following phase transition behavior and physical properties. Furthermore, the elemental analysis results were similar to those of the second
As shown in the table.

Response time: 104 μs (39°C) Tilt angle (2θ): 77° (39°C) −Polyaddition reaction− 10 mmol of the diene compound (59) obtained in [5], 1,
A toluene solution containing 10 mmol of 1,3,3-tetramethyldisiloxane and 20 mg of hexachloroplatinic acid hexahydrate was stirred under argon gas at 80°C for 24 hours. The reaction mixture was concentrated and purified by column chromatography to obtain the desired copolymer (yield: 66%). The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown in Table 1, and its IR spectrum in Figure 14.

Example 15 Carboxylic acid derivative (22) obtained in Example 5-[3]
43.2 g of thionyl chloride, 34 ml of thionyl chloride, and 130 ml of toluene were placed in a 1000 ml four-neck flask equipped with a reflux condenser, and the mixture was stirred to form a homogeneous solution.
After the addition, the reaction temperature was raised to 65°C and the mixture was heated and stirred for 4 hours.

After this, the reaction mixture was aspirated under reduced pressure.
The mixture was heated at 65°C for 1 hour and then at 80°C for 30 minutes to remove toluene and remaining thionyl chloride. After cooling to room temperature, 170 ml of toluene and 11.8 ml of pyridine were added to the reaction mixture to form a homogeneous solution. To this solution, 170 ml of a toluene solution containing 37.9 g of optically active 1-methylheptyl 4'-hydroxybiphenyl-4-carboxylate was added dropwise over 30 minutes with stirring. The mixture was then stirred overnight at room temperature to complete the reaction.

The reaction mixture was filtered to remove precipitated pyridine salts, and the filtrate was then placed on a rotary evaporator.
The solvent was distilled off under reduced pressure at a bath temperature of 50°C to obtain 79.8 g of a concentrate. Then, 80 g of methylene chloride was added to the concentrate and stirred to prepare a homogeneous, transparent solution. This solution was separated by liquid chromatography using a pre-column packed with activated alumina and a main column packed with silica gel. The eluate containing the target product was placed on a rotary evaporator, and the solvent was distilled off under reduced pressure at a bath temperature of 50°C to obtain 69.2 g of the crude product of the target diene compound (60).
The crude product was transferred to a 1-liter flask and 900 ml of ethanol was added.
Attach a reflux condenser to the flask and heat to 70°C.
The mixture was stirred at room temperature for 10 minutes. After confirming that the white solid had completely dissolved and become a homogeneous solution, the flask was allowed to cool naturally to near room temperature. Next, the flask was stoppered, and after preventing moisture from entering, it was placed in a refrigerator and left to stand for at least 4 hours. After this, the flask was removed, and the precipitated white solid was collected by suction filtration and washed several times with ethanol.
Finally, the solid was dried overnight in a vacuum oven at 50°C to obtain the desired diene compound (60) in an amount of 57.8 g (74% yield).

This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are also shown below.

Cry or Response time: 25 μs (52°C) Tilt angle (2θ): 81° (52°C) -Polyaddition reaction- 57.8 g of the diene compound (60) obtained above and 7.6 g of 1,1,3,3-tetramethyldisiloxane were dissolved in 430 ml of toluene, and 6 mg of chloroplatinic acid hexahydrate was added in an argon gas stream.
was added as a catalyst and the reaction was carried out at 80°C for 8 hours.

After the reaction was complete, the mixture was allowed to cool to room temperature, and 1.3 g of activated carbon was added to the reaction mixture. The mixture was then stirred at 50°C for 10 minutes and filtered to remove the activated carbon. The toluene was removed from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 50.3 g of the desired liquid crystalline copolymer. The molecular weight, phase transition temperature, and response time of the resulting copolymer are shown below. The IR spectrum of the resulting copolymer is shown in Figure 15.

Cry or Response time: 2.0 ms (63°C), 8.2 ms (43°C), 43 ms (23°C) Mn = 2800 Example 16 Carboxylic acid derivative (22) obtained in Example 5-[3]
The same procedure as in Example 15 was repeated except that 44.4 g of the above diene compound (61) was used, and 30.5 g of optically active 1-methylbutyl 4'-hydroxybiphenyl-4-carboxylate was used.
obtained.

This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. The results of elemental analysis are also shown below.

Cry or Response time: 41 μs (68°C) Tilt angle (2θ): 74° (68°C) -Polyaddition reaction- 44.4 g of the diene compound (61) obtained above and 6.2 g of 1,1,3,3-tetramethyldisiloxane were dissolved in 330 ml of toluene, and 5 mg of chloroplatinic acid hexahydrate was added in an argon gas stream.
is added as a catalyst and the reaction is carried out at 80°C for 8 hours.

The same treatment and purification as in Example 15 were carried out to obtain 36.5 g of the target liquid crystalline copolymer. The molecular weight, phase transition temperature, and response time of the obtained copolymer are shown below. The IR spectrum of the obtained copolymer is shown in Figure 16.

Response time: 0.4 ms (91°C), 0.9 ms (71°C), 3.2 ms (51°C) Mn = 2400 Example 17 7.1 g (15.8%) of the carboxylic acid derivative (63) represented by the following formula
millimolar), Thionyl chloride 8 ml, pyridine 0.5 ml, methylene chloride 50 ml
The mixture was collected in a flask equipped with a reflux condenser and heated with stirring for 4 hours.

Thereafter, the solvent and the like were removed under reduced pressure at 65°C using an aspirator. Next, 50 ml of toluene was added to the reaction mixture that had been cooled to room temperature. 3.56 g (17.1%) of optically active (S)-1-methylbutyl 4-hydroxybenzoate was added thereto.
1.54 g (19.5 mmol) of pyridine and 50 ml of toluene were added, and the mixture was stirred at room temperature for 16 hours.

Next, the solid matter was removed, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography.
The target diene compound (62) 6.78 g (10.6 mmol)
The yield was 67%.

-Polyaddition reaction- Copolymer with 3 g (4.7 mmol) of the diene compound (62) obtained above
0.42 g (3.1 mmol) of this and 1,1,3,3-tetramethyldisiloxane were dissolved in 20 ml of toluene, and 3 mg (0.0058 mmol) of chloroplatinic acid hexahydrate was added as a catalyst in an argon gas stream, followed by reaction at 80° C. for 20 hours.

After the reaction was completed, toluene was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2.9 g of the target liquid crystalline copolymer. The molecular weight, phase transition temperature, and response time of the obtained copolymer are shown below.
The ¹ H-NMR spectrum of the resulting copolymer is shown in FIG.

Response time: 3.17 ms (25°C) Mn = 1545 Mw = 2279 Mw/Mn = 1.48 Tilt angle (2θ) = 66° (25°C) Example 18 Carboxylic acid derivative (27) obtained in Example 7-[2]
1.76 g (3.7 mmol) of thionyl chloride and 8 ml of thionyl chloride were placed in a flask equipped with a reflux condenser and heated to 60°C for 4.5 minutes.
Heating and stirring were continued for 1 hour. Then, excess thionyl chloride was distilled off under reduced pressure using an aspirator equipped with a dry ice/methanol trap, and 10 ml of toluene was added to the reaction mixture cooled to room temperature.
-1-Methylheptyl 4-hydroxybenzoate 0.
93g (3.7mmol), pyridine 0.37g (4.7mmol),
10 ml of toluene was added, and the mixture was stirred at room temperature for 15 hours to complete the reaction.

Next, the solid matter was removed, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography.
The target diene compound (64) was obtained in an amount of 1.86 g (2.6 mmol, yield 70%).

-Polyaddition reaction- A copolymer of 1.84 g (2.6 mmol) of the diene compound (64) obtained above and 0.23 g (1.7 mmol) of 1,1,3,3-tetramethyldisiloxane was prepared.
The resulting mixture was dissolved in 14 ml of toluene, and 2 mg of chloroplatinic acid hexahydrate was added as a catalyst in an argon gas stream, followed by reaction at 80° C. for 20 hours under an argon gas stream.

After the reaction was completed, toluene was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.7 g of the target liquid crystalline copolymer. The molecular weight, phase transition temperature, and response time of the obtained copolymer are shown below.
The ¹ H-NMR spectrum of the resulting copolymer is shown in FIG.

Response time: 6.8 ms (25°C) Mn = 2243 Mw = 3850 Mw/Mn = 1.72 Tilt angle (2θ) = 70° (25°C) The repeating units, phase transition temperatures, number average molecular weights, and response times of the copolymers obtained in Examples 15 to 18 are summarized in Table 3.

Example 19 To a stirred solution of 0.18 mol of sodium hydride in 200 mL of THF, 0.18 mol of 1,6-heptadiene-4-ol was added dropwise at room temperature, followed by dropwise addition of 0.25 mol of 1,10-dibromodecane. After refluxing for 15 hours, the reaction mixture was filtered, concentrated, and purified by silica gel column chromatography to obtain 48 mmol of the desired ether (65) (yield: 27%).

45 mmol of the ether (65) obtained in [1], 4-
A solution of 54 mmol of methyl hydroxybenzoate and 160 mmol of potassium carbonate in 100 mL of 2-butanone was refluxed for 10 hours. The reaction mixture was filtered, concentrated, and purified by silica gel column chromatography to give the desired ester (66) (yield 75%).

32 mmol of the ester (66) obtained in [2], 91 mmol of potassium hydroxide, 30 ml of methanol, and 70 ml of water were refluxed for 6 hours. The reaction mixture was added to 300 ml of water and adjusted to pH 1 with concentrated hydrochloric acid.
The precipitated solid was filtered off, washed with water, and then
The target compound (67) was obtained (yield
96%).

20 ml of thionyl chloride was added to 31 mmol of the compound (67) obtained in [3], and the mixture was stirred at 60°C for 3 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain the acid chloride. This acid chloride was dissolved in 50 ml of toluene, and 32 ml of 4'-hydroxybiphenyl-4-carboxylic acid 1-methylbutyl ester was added thereto.
A solution of 39 mmol of pyridine and 100 ml of toluene was added dropwise at room temperature, and the mixture was stirred at room temperature for 15 hours. After filtering off the solid matter, the solvent was distilled off under reduced pressure. The residue was purified by alumina and then silica gel column chromatography to obtain the target diene compound (68) (yield 78%).
%).

This ^diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties.
The NMR spectrum is shown in FIG. 19 and the elemental analysis data are shown in Table 4.

Response time: 10 μs (60°C), 32 μs (40°C), 98 μs (25°C) Tilt angle (2θ): 74° (25°C) -Polyaddition reaction- 1.6 mmol of the diene compound (68) obtained in [4],
A solution of 1.0 mmol of 1,1,3,3-tetramethyldisiloxane and 2 mg of hexachloroplatinic acid hexahydrate in 8 mL of toluene was stirred under an argon atmosphere at 85° C. for 8 hours. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the desired copolymer (conversion rate 84%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 20.

Example 20 Diene compound (68) obtained in Example 19-[4] and copolymer
millimolar, 1,1,3,3,5,5-hexamethyltrisiloxane
A solution of 1.1 mmol of hexachloroplatinic acid hexahydrate and 2 mg of hexachloroplatinic acid hexahydrate in 8 mL of toluene was stirred for 8 hours at 85° C. under an argon atmosphere. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the target copolymer (conversion rate 80%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 21.

Example 21 Diene compound (68) obtained in Example 19-[4]
mmol, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane 0.7 mmol, hexachloroplatinic acid hexahydrate 2 mg
A 10 ml toluene solution of the above was stirred for 10 hours at 85° C. under an argon atmosphere. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the target copolymer (conversion rate 78%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 22.

Example 22 To a stirred solution of 52 mmol of sodium hydride in 50 mL of THF, 47 mmol of 1,8-nonadien-5-ol was added dropwise at room temperature, followed by dropwise addition of 94 mmol of 1,10-dibromodecane. After refluxing for 21 hours, the reaction mixture was filtered, concentrated, and purified by silica gel column chromatography to obtain 15 mmol of the desired ether (69) (yield 32%).
%).

8.3 mmol of the ether (69) obtained in [1], 4
A solution of 10 mmol of methyl 2-hydroxybenzoate and 30 mmol of potassium carbonate in 50 mL of 2-butanone was refluxed for 10 hours. The reaction mixture was filtered and concentrated, and then purified by silica gel column chromatography to obtain the desired ester (70) (yield 65%).

[0112] 5.4 mmol of the ester (70) obtained in [2], 16 mmol of potassium hydroxide, 6 ml of methanol, and 14 ml of water were added to 5
The reaction mixture was added to 100 ml of water and adjusted to pH =
The precipitated wax-like substance was washed with water and then dried under reduced pressure at 30°C to obtain the target compound (71) (yield 95%).

5.1 mmol of the compound (71) obtained in [3] was added to 5 ml of thionyl chloride and stirred at 60°C for 4 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain the acid chloride. This acid chloride was dissolved in 5 ml of toluene, and 4'-hydroxybiphenyl-4-carboxylic acid 1-methylbutyl ester was added thereto.
A 20 ml solution of 5.5 mmol of toluene and 6.4 mmol of pyridine was added dropwise at room temperature, and the mixture was stirred at room temperature for an additional 18 hours. After filtering off the solid matter, the solvent was distilled off under reduced pressure. The residue was purified by alumina and then by silica gel column chromatography to obtain the target diene compound (72) (yield 61%).
%).

This ^diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties.
The NMR spectrum is shown in FIG. 23, and the results of elemental analysis are shown in Table 4.

Response time: 6.9 μs (60°C), 19 μs (40°C), 56 μs (25°C) Tilt angle (2θ): 74° (25°C) -Polyaddition reaction- 0.9 mmol of the diene compound (72) obtained in [4],
A 6 mL toluene solution containing 0.6 mmol of 1,1,3,3-tetramethyldisiloxane and 1 mg of hexachloroplatinic acid hexahydrate was stirred under an argon atmosphere at 85°C for 10 hours. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the desired copolymer (conversion rate 64%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 24.

Example 23 To a stirred solution of 0.18 mol of sodium hydride in 200 mL of THF, 0.18 mol of 1,5-hexadiene-3-ol was added dropwise at room temperature, followed by dropwise addition of 0.36 mol of 1,10-dibromodecane. After refluxing for 15 hours, the reaction mixture was filtered, concentrated, and purified by silica gel column chromatography to obtain 60 mmol of the desired ether (73) (yield: 33%).

45 mmol of the ether (73) obtained in [1], 4-
A solution of 54 mmol of methyl hydroxybenzoate and 160 mmol of potassium carbonate in 100 mL of 2-butanone was refluxed for 10 hours. The reaction mixture was filtered and concentrated, and then purified by silica gel column chromatography to obtain the desired ester (74) (yield 72%).

32 mmol of the ester (74) obtained in [2], 91 mmol of potassium hydroxide, 30 ml of methanol, and 70 ml of water were refluxed for 6 hours. The reaction mixture was added to 300 ml of water and adjusted to pH 1 with concentrated hydrochloric acid.
The precipitated solid was filtered off, washed with water, and then
The resulting mixture was dried under reduced pressure at 20°C to obtain the target compound (75) (yield
90%).

20 ml of thionyl chloride was added to 25 mmol of the compound (75) obtained in [3], and the mixture was stirred at 80°C for 3 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in 50 ml of toluene, and 30 ml of 4'-hydroxybiphenyl-4-carboxylic acid 1-methylbutyl ester was added thereto.
A solution of 35 mmol of pyridine and 100 ml of toluene was added dropwise at room temperature, and the mixture was stirred at room temperature for 15 hours. After filtering off the solid matter, the solution was evaporated under reduced pressure. The residue was purified by alumina and then by silica gel column chromatography to obtain the target diene compound (76) (yield 76%).
%).

This ^diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties.
The NMR spectrum is shown in FIG. 25, and the results of elemental analysis are shown in Table 4.

Response time: 41 μs (68°C) Tilt angle (2θ): 74° (68°C) -Polyaddition reaction- 1.6 mmol of the diene compound (76) obtained in [4],
1.0 mmol of 1,1,3,3,5,5-hexamethyltrisiloxane and 2 mg of hexachloroplatinic acid hexahydrate in 1% toluene
The resulting 0 ml solution was stirred for 8 hours at 85° C. under an argon atmosphere. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the target copolymer (conversion rate 82%).

The molecular weight, phase transition temperature, and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 26.

Example 24 Diene compound (76) obtained in Example 23-[4] and copolymer
A 10 ml toluene solution containing 1.1 mmol of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1.1 mmol of hexachloroplatinic acid hexahydrate, and 2 mg of hexachloroplatinic acid hexahydrate was heated at 85° C. under an argon atmosphere.
The mixture was stirred for 9 hours at rt The reaction mixture was concentrated and then purified by silica gel column chromatography to obtain the desired copolymer (conversion rate: 86%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 27.

Example 25 To a stirred solution of 55 mmol of sodium hydride in 50 mL of THF, 50 mmol of 1,10-undecadien-6-ol was added dropwise at room temperature, followed by the dropwise addition of 100 mmol of 1,10-dibromodecane. After refluxing for 12 hours, the reaction mixture was filtered, concentrated, and purified by silica gel column chromatography to obtain 15 mmol of the desired ether (77) (yield 30%).

15 mmol of the ether (77) obtained in [1], 4-
A solution of 17 mmol of methyl hydroxybenzoate and 20 mmol of potassium carbonate in 50 mL of 2-butanone was refluxed for 15 hours. The reaction mixture was filtered and concentrated, and then purified by silica gel column chromatography to obtain the desired ester (78) (yield 78%).

11 mmol of the ester (78) obtained in [2], 30 mmol of potassium hydroxide, 6 ml of methanol, and 14 ml of water were refluxed for 5 hours. The reaction mixture was added to 100 ml of water and adjusted to pH 1 with concentrated hydrochloric acid.
The resulting mixture was extracted twice with 50 ml of ether. The combined ether layers were dried over magnesium sulfate and
The solvent was removed by distillation under reduced pressure to obtain the target compound (79) (yield 61%).

5 ml of thionyl chloride was added to 0.7 mmol of the compound (79) obtained in [3], and the mixture was stirred at 80°C for 2 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain the acid chloride. This acid chloride was dissolved in 10 ml of toluene, and a solution of 7 mmol of 4'-hydroxybiphenyl-4-carboxylic acid 1-methylbutyl ester and 10 mmol of pyridine in 20 ml of toluene was added dropwise at room temperature, and the mixture was stirred at room temperature for an additional 18 hours. After filtering off the solid matter, the solvent was distilled off under reduced pressure. The residue was purified by alumina and then by silica gel column chromatography to obtain the desired diene compound (80) (yield 65%).
%).

This ^diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties.
The NMR spectrum is shown in FIG. 28, and the results of elemental analysis are shown in Table 4.

Response time: 17 μs (60°C), 44 μs (40°C), 124 μs (25°C) Tilt angle (2θ): 81° (25°C) -Polyaddition reaction- 0.9 mmol of the diene compound (80) obtained in [4],
A 15 ml toluene solution containing 0.6 mmol of 1,1,3,3-tetramethyldisiloxane and 1 mg of hexachloroplatinic acid hexahydrate was stirred under an argon atmosphere at 85° C. for 8 hours. The reaction solution was concentrated and then purified by silica gel column chromatography to obtain the desired copolymer (conversion rate 65%).

The molecular weight, phase transition temperature and response time of the copolymer obtained are shown in Table 5. The ¹ H-NMR spectrum of this copolymer is shown in Figure 29.

INDUSTRIAL APPLICABILITY The liquid crystal copolymer obtained by the present invention exhibits ferroelectricity over a wide temperature range including room temperature, and responds quickly to an external electric field, making it suitable for use in various electro-optical devices in the field of optoelectronics, and can also be advantageously used as a display element for large screens or curved screens.

───────────────────────────────────────────────────────── Continued from the front page (51) Int.Cl. ⁶ Identification symbol Internal reference number FI Technical marking location C07C 69/94 9546-4H C07D 239/26 239/28 239/34 C08G 77/42 NUK C09K 19/40 9279-4H

Claims (18)

[Claims] Claim 1: A repeating unit represented by the following general formula: wherein r and p are integers of 2 to 5, q is an integer of 0 to 3,
m is an integer from 1 to 20, and ^R where ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 , and ^R3 is ^R4 and ^R5 are _-CH3 or a halogen atom, and a and d are 0 to
10, and b is 0 or 1 (when ^R5 is _-CH3 , d is not 0).
I] is a liquid crystalline copolymer with a molar ratio of approximately 1:1. 2. The liquid crystal copolymer according to claim 1, having a number average molecular weight of 1,000 to 1,000,000. [Claim 3] R ¹ is 3. The liquid crystal copolymer according to claim 2, which is selected from the group consisting of: [Claim 4] ^R3 is 4. The liquid crystal copolymer according to claim 3, which is selected from the group consisting of: Claim 5: A repeating unit represented by the following formula: and a repeating unit represented by the following formula: 3. The liquid crystal copolymer according to claim 2, comprising: Claim 6: A repeating unit represented by the following formula: and a repeating unit represented by the following formula: 3. The liquid crystal copolymer according to claim 2, comprising: 7. A repeating unit represented by the following formula: and a repeating unit represented by the following formula: 3. The liquid crystal copolymer according to claim 2, comprising: 8. A repeating unit represented by the following formula: and a repeating unit represented by the following formula: 3. The liquid crystal copolymer according to claim 2, comprising: 9. A repeating unit represented by the following formula: and a repeating unit represented by the following formula: 3. The liquid crystal copolymer according to claim 2, comprising: Claim 10: A diene compound represented by the following general formula: [wherein r and p are integers of 2 to 5, R ¹ is where ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 ;
^R3 is ^R4 and ^R5 are _-CH3 or a halogen atom, and a and d are 0 to
10, and b is 0 or 1 (when ^R5 is _-CH3 , d is not 0). ] and a silicon compound represented by the following general formula 2. A method for producing a liquid crystal copolymer according to claim 1, characterized in that a hydrosilylation reaction is carried out in a solvent in the presence of a catalyst with (wherein q is an integer of 0 to 3) in an approximately equimolar ratio. Claim 11: A compound represented by the following general formula: wherein r and p are integers of 2 to 5, R ¹ is where ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 ;
^R3 is ^R4 and ^R5 are _-CH3 or a halogen atom, and a and d are 0 to
10, and b is 0 or 1 (when ^R5 is _-CH3 , d is not 0). Claim 12: R ¹ is 12. The diene compound according to claim 11, which is selected from the group consisting of: Claim 13: ^R3 is 13. The diene compound according to claim 12, which is selected from the group consisting of: Claim 14: A compound of the following formula: The diene compound according to claim 11, represented by the formula: Claim 15: A compound of the following formula: The diene compound according to claim 11, represented by the formula: Claim 16: A compound represented by the following formula: The diene compound according to claim 11, represented by the formula: [Claim 17] General formula (wherein r and p are integers of 2 to 5) and an alcohol represented by the general formula X(CH ₂ ) _m X (wherein m is an integer of 1 to 20, and X is -Br, -I, or In a solvent, in the presence of an alkaline reagent, an etherification reaction is carried out, and the resulting reaction mixture is purified to obtain a product, which is then mixed with a bifunctional compound represented by the general formula HO-R ¹ (wherein R ¹ is where ^R2 is ^-COOR3 , ^-OR3 or ^-OCOR3 ;
^R3 is ^R4 and ^R5 are _-CH3 or a halogen atom, and a and d are 0 to
12. The method for producing a diene compound according to claim ₁₁ , characterized in that an etherification reaction is carried out with a hydroxy compound represented by the formula (I) in a solvent in the presence of an alkaline reagent, wherein ^R is an integer of 0 to 10, and b is 0 or 1 (when R is -CH3, d is not 0). [Claim 18] General formula (wherein r and p are integers of 2 to 5) and an alcohol represented by the general formula X(CH ₂ ) _m X (wherein m is an integer of 1 to 20, and X is -Br, -I, or In a solvent, in the presence of an alkaline reagent, an etherification reaction is carried out with a bifunctional compound represented by the general formula (wherein e is 1 or 2) in a solvent in the presence of an alkaline reagent,
The reaction mixture obtained by the etherification reaction is filtered, and the resulting product is hydrolyzed in alkali, water, or alcohol. The resulting reaction solution is poured into water, and a mineral acid is added to make the pH acidic. The solution is then extracted with ether. The ether is removed, and the resulting solid is reacted with an acid halide agent to obtain an acid chloride and a compound of the general formula HO-AR ² (wherein A is 12. The method for producing a diene compound according to claim 11, characterized in that an esterification reaction is carried out in a solvent with a hydroxy compound represented by the formula: