JPH0860156A - Optically active compound - Google Patents

Abstract

PURPOSE: To obtain anti-ferroelectric liquid crystal excellent in display characteristics and useful ad a liquid crystal electrooptical element for printer shutter array, a liquid crystal display, etc. CONSTITUTION: A compound of formula I [(m) is 6-14; (n) is 3-10; X is a single bond, O or CO2 ; Y is H or F], e.g., (R)-4'-decyloxy-3-fluoro-4-diphenylcarboxylic acid-4-(1-methylheptyloxycarbonyl)-penyl ester. The compound of formula I (X is O) is obtained according to the scheme of formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antiferroelectric liquid crystal material showing a chiral smectic C _A phase (hereinafter abbreviated as S _mCA ^* ) having three stable states, a liquid crystal display and a printer shutter array using the same. The present invention relates to a novel optically active compound that can be used in the liquid crystal electro-optical element, and an antiferroelectric liquid crystal composition containing the same.

[0002]

2. Description of the Related Art In recent years, liquid crystal displays are thin, lightweight, and
It has come to be widely used as a display element by taking advantage of features such as low power consumption, but most of these display devices use TN (Twisted) which uses nematic liquid crystal.
d Nematic) type is generally adopted. Since the driving of this TN type display method is based on the anisotropy of the relative dielectric constant of the liquid crystal, the response speed thereof is slow and the need for improvement has been pressing.

On the other hand, a chiral smectic C ^* phase (S) having ferroelectricity found by Meyer et al.
A liquid crystal device using a liquid crystal having abbreviated mC ^* ) has a high-speed response and a memory property that cannot be achieved by a nematic liquid crystal, and by utilizing these characteristics, application to a ferroelectric liquid crystal display. Research is done vigorously. However, it is difficult to realize the good orientation and memory properties required for this display method in an actual display, and there are problems such as being vulnerable to external shock, and there are many problems to be solved. Remaining.

On the other hand, recently, Chandani et al. Discovered an antiferroelectric phase (SmC _A ^* phase) exhibiting a tristable state on the low temperature side of the SmC ^* phase. This SmC
_{The A} ^* phase is a thermodynamically stable phase in which dipoles are arranged antiparallel to each adjacent layer, and has a clear threshold value and double hysteresis characteristic with respect to the applied voltage. An electric field-induced phase transition occurs between the ferroelectric phase and the ferroelectric phase. By applying this switching behavior, a new display method (for example,
Liquid crystal display) is under consideration.

[0005]

The relationship between the applied voltage and the amount of transmitted light in an anti-ferroelectric liquid crystal display device using an anti-ferroelectric liquid crystal shows a double hysteresis characteristic as shown in FIG. This figure shows an antiferroelectric liquid crystal prepared by injecting an antiferroelectric liquid crystal material into a cell obtained by providing transparent electrodes and laminating two glass substrates whose surfaces have been oriented with a spacer in between. The display element is installed in a polarization microscope with a photomultiplier, a triangular wave voltage is applied to the element under a crossed Nicols, and the change in transmitted light at that time is measured. Response from the dark display state by taking advantage of this double hysteresis characteristic to the bright display state is achieved when exceeding the threshold value V ₁ in the process of raising the applied voltage in FIG. 1, the dark display state from the bright display state The response to is achieved when the applied voltage drops below the threshold value V _{2 in the} process of decreasing. Further, since the threshold value V ₁ in the process of increasing the voltage and the threshold value V ₂ in the process of decreasing the voltage are different, the antiferroelectric liquid crystal display device has a memory property, and therefore V ₂
In the voltage between ~V ₁ but display state of a bright or dark is maintained, the voltage width of (V ₁ -V ₂₎ is not sufficiently large, the response to the small voltage opposite respective display states by the change of Resulting in. Therefore, the hysteresis width (V ₁ −
It can be said that the anti-ferroelectric liquid crystal having excellent display characteristics has a double hysteresis characteristic with large V ₂ ).

Further, the liquid crystal display must operate even in a considerably high temperature range depending on the use environment. For example, in a liquid crystal display for automobiles, the temperature becomes close to 100 ° C. under direct sunlight. Under these circumstances, antiferroelectric liquid crystals with excellent display characteristics in a wide temperature range from high temperature to room temperature are required, but currently there are few types of antiferroelectric liquid crystals, and they are particularly excellent. Few have display characteristics.

The present invention provides a novel antiferroelectric liquid crystal having excellent display characteristics and a chemical structure different from that of the conventional one.

[0008]

The present invention provides the following general formula (1) or (2)

[0009]

[Chemical 6]

[In the formula (1), m and n are each 6 ≦ m ≦ 1.
4,3 ≦ n ≦ 10, X is a single bond, O
And COO, Y is H or F, and * represents an asymmetric carbon atom. ]

[0011]

[Chemical 7]

[In the formula (2), m and n are each 6 ≦ m ≦ 1.
4,3 ≦ n ≦ 10, X is a single bond, O
And COO, and A is

[0013]

Embedded image

And B is

[0015]

[Chemical 9]

Any one of the above, and * represents an asymmetric carbon atom. ] An antiferroelectric liquid crystal composition containing the optically active compound represented by the formula [1] and at least one of the optically active compounds represented by the formulas (1) and (2).

Here, the content of the optically active compound represented by the formulas (1) and (2) in the antiferroelectric composition is 5% by weight or more in order to improve the display characteristics. Is preferred.

An example of a method for producing the object compound of the present invention is shown by a reaction formula as follows. Regarding the compound represented by the general formula (1), for example, Mol. Cryst. Li
q. Cryst. , 1989, Vol. 172, 165-1
After synthesizing the carboxylic acid by a known synthesis method such as 89,
An object compound can be obtained by performing an esterification reaction with an optically active hydroxybenzoic acid ester.

[0019]

[Chemical 10]

In the reaction 1, after the Grignard reagent was converted to an organoboron compound with trimethoxyborane, 4-bromo-2 was used.
The reaction is carried out using fluorobenzonitrile and a palladium catalyst. Reaction 2 uses boron tribromide to demethylate. Reaction 3 is an alkyl halide in DMF,
The reaction is carried out using a base such as sodium hydride. R in the formula
Is C _m H _{2m + 1} . In reaction 4, hydrolysis is carried out in the usual manner. Reaction 5 is carried out in methylene chloride using a condensing agent such as DCC (dicyclohexylcarbodiimide) and a base such as dimethylaminopyridine.

In the above reaction formula, the case where -X- is -O- is described, but when -X- is a single bond, this method can be applied to easily synthesize. Also, -X- is -COO-
The compound can be obtained by, for example, the following synthetic method.

[0022]

[Chemical 11]

Reaction 6 is a conventional hydrolysis. Reaction 7 is an esterification reaction according to a conventional method. Here, R is C _m H _{2m + 1} .

With respect to the compound represented by the general formula (2), for example, a carboxylic acid is synthesized by a known synthesis method such as Japanese Examined Patent Publication (Kokoku) No. 55-6631 and then subjected to an esterification reaction with an optically active hydroxybenzoic acid ester, The target compound can be obtained.

[0025]

[Chemical 12]

Where R is --X--C _m H _{2m + 1} , where X is a single bond or --O--. Y is H or F (the same applies hereinafter). Reaction 8 is carried out by using a base such as sodium methoxide in methanol. Reaction 9 is hydrolyzed as usual. Reaction 10 is DC in methylene chloride
The reaction is carried out using a condensing agent such as C and a base such as dimethylaminopyridine. Further, a compound in which -X- is -COO- can be synthesized by the following synthetic method.

[0027]

[Chemical 13]

In reaction 11, debenzylation is carried out by hydrogenation using a palladium carbon catalyst. In reaction 12, an esterification reaction is carried out in the usual way. Here, R is C _m H _{2m + 1} . Reaction 10 is the same as above.

[0029]

Embedded image

When R ¹ is alkyl (C _m H _{2m + 1} ) or alkoxy (C _m H _{2m + 1} O), it is as defined in the above formula. Here, as R ¹ , alkanoyloxy (C _m H
When introducing _2m + 1 COO-) is started using a benzyloxy _{(C 6 H 5 -CH 2 -O-} ) at the R ^1, the reaction was carried out 13 and 14, then the following reaction 15 ~ 1
Continue to 8 and 10.

[0031]

[Chemical 15]

Reaction 10 is carried out in methylene chloride using a condensing agent such as DCC and a base such as dimethylaminopyridine. Reaction 13 is a reaction with diethyl ethoxymethylenemalonate in methanol using a base such as sodium methoxide. In the reaction 14, after chlorination with phosphorus oxychloride or the like, hydrogenation and dechlorination are performed using a palladium carbon catalyst, and then the ester is hydrolyzed. Reaction 1
For No. 5, benzyl bromide and a base such as potassium hydrogen carbonate are reacted in DMF. Reaction 16 performs esterification in a conventional manner. In the reaction 17, a palladium carbon catalyst is used for hydrogenation and debenzylation.

[0033]

INDUSTRIAL APPLICABILITY The present invention provides a novel antiferroelectric liquid crystal having excellent display characteristics. The novel optically active compounds and the antiferroelectric liquid crystal composition containing them provided by the present invention are useful for devices such as liquid crystal displays and printer shutter arrays to which the switching behavior peculiar to the antiferroelectric phase is applied. is there.

[0034]

The present invention will be described in more detail with reference to the following examples. The identification of the chemical structure of the target compound in the examples was carried out by NMR, IR, and optical rotation measurement, and the phase transition temperature measurement and the phase identification were carried out by DSC and polarization microscope observation. The method of observing with a polarization microscope is described below. After applying polyimide to a glass substrate provided with two transparent electrodes, rubbing treatment was performed, and the glass substrate was attached to the cell at a distance of 2 μm with a spacer, and the target compound obtained in each Example and The composition was injected to prepare a liquid crystal thin film cell. The prepared liquid crystal cell was placed in a polarizing microscope with a hot stage in which two polarizing plates were orthogonal to each other so as to have a dark field at an applied voltage of 0 V, and the phase transition temperature was measured and the phase was identified.

In addition, Examples 1, 2, 8, 9, 14 to 17
The optical response double hysteresis characteristic of the compound and composition of the above is arranged in a polarizing microscope with a photomultimeter in which two polarizing plates are orthogonal to each other so that the cell has a dark field at an applied voltage of 0 V. A triangular wave voltage of 1 Hz was applied to this liquid crystal cell for measurement.

Example 1 ((R) -4'-decyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylheptyloxycarbonyl) phenyl ester)

[0037]

Embedded image

4'-decyloxy-3-fluoro-4-
1.50 g of biphenylcarboxylic acid, 1.00 g of (R) -hydroxybenzoic acid-1-methylheptyl ester,
0.03 g of N, N-dimethyl-4-aminopyridine was dissolved in 28.6 ml of methylene chloride at room temperature, 0.93 g of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for one day. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain 1.70 g of the objective compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.88 (m, 3H), 0.92-1.84
(M, 30H), 4.02 (t, 2H), 5.16
(M, 1H), 6.99 (m, 2H), 7.30-7.
59 (m, 4H), 8.12 (m, 3H). IR spectrum (KBr method, cm ^-1 ): 2926,285
4,1730,1606,1282,1209,116
3,1114. Specific rotation [α] _D ²⁰ = -21.55 ° (C, 2.00,
in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0040]

[Equation 1]

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 2 shows the optical response double hysteresis characteristic of the target compound at 80 ° C. The compound shows a good double hysteresis characteristic.

(Example 2) ((R) -4'-decyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0043]

[Chemical 17]

4'-decyloxy-3-fluoro-4-
Biphenylcarboxylic acid 1.40 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester 1.41 g, N, N-dimethyl-4-aminopyridine 0.03 g in methylene chloride 33.5 ml. After dissolving at room temperature, dicyclohexylcarbodiimide 0.87 g
Was added and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to give the target compound 1.6.
0 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.88 (m, 6H), 1.10-1.83
(M, 34H), 4.02 (t, 2H), 5.18
(M, 1H), 7.00 (m, 2H), 7.13 (m,
2H), 7.40 (m, 1H), 7.47 (m, 2
H), 8.01 (m, 1H), 8.11 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2928,285
5,1737,1708,1609,1282,125
One. Specific rotation [α] _D ²⁰ = -18.76 ° (C, 2.02
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0046]

[Equation 2]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 3 shows the optical response double hysteresis characteristic of the target compound at 90 ° C. The compound shows a good double hysteresis characteristic.

(Example 3) ((R) -4'-heptyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0049]

Embedded image

4'-heptyloxy-3-fluoro-4
-Biphenylcarboxylic acid 1.50 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester 1.22 g, N, N-dimethyl-4-aminopyridine 0.03 g methylene chloride 32.1 ml Dicyclohexylcarbodiimide 1.09
g was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to give the target compound 1.5.
0 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.91 (m, 6H), 1.20-
1.84 (m, 23H), 4.02 (t, 2H), 5.
18 (m, 1H), 6.99 (m, 2H), 7.13
(M, 2H), 7.38 (m, 1H), 7.46 (m,
1H), 7.57 (m, 2H), 8.00 (m, 1
H), 8.10 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2926,285
8,1730,1609,1297,1255,113
6. Specific rotation [α] _D ²⁰ = -20.29 ° (C, 2.01
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0052]

(Equation 3)

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 80 ° C.

(Example 4) ((R) -4'-octyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0055]

[Chemical 19]

4'-octyloxy-3-fluoro-4
-Biphenylcarboxylic acid 1.50 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester 1.14 g, N, N-dimethyl-4-aminopyridine 0.03 g methylene chloride 30.9 ml In room temperature at room temperature and then dicyclohexylcarbodiimide 1.00
g was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to give the target compound 1.6.
0 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.90 (m, 6H), 1.29-
1.84 (m, 25H), 4.02 (t, 2H), 5.
18 (m, 1H), 7.00 (m, 2H), 7.13
(M, 2H), 7.40 (m, 1H), 7.47 (m,
1H), 7.57 (m, 2H), 8.01 (m, 1
H), 8.11 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2927,285
8, 1732, 1615, 1433, 1286, 125
One. Specific rotation [α] _D ²⁰ = -20.63 ° (C, 2.05
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0058]

[Equation 4]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 85 ° C.

(Example 5) ((R) -4'-nonyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0061]

Embedded image

4'-nonyloxy-3-fluoro-4-
1.50 g of biphenylcarboxylic acid, 1.12 g of (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester and 0.03 g of N, N-dimethyl-4-aminopyridine in 29.6 ml of methylene chloride. After dissolving at room temperature, dicyclohexylcarbodiimide 0.96 g
Was added and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallized from ethanol to obtain the target compound 1.2.
6 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.87-0.89 (m, 6H), 1.29-
1.84 (m, 27H), 4.02 (t, 2H), 5.
18 (m, 1H), 7.00 (m, 2H), 7.13
(M, 2H), 7.39 (m, 1H), 7.46 (m,
1H), 7.57 (m, 2H), 8.00 (m, 1
H), 8.10 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2927,285
7,1732,1615,1434,1402,128
5,1158,1133. Specific rotation [α] _D ²⁰ = -18.87 ° (C, 2.04
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0064]

(Equation 5)

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 85 ° C.

(Example 6) ((R) -4'-undecyloxy-3-fluoro-4-biphenylcarboxylic acid-4)
-(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0067]

[Chemical 21]

4'-undecyloxy-3-fluoro-
4-biphenylcarboxylic acid 1.50 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester 1.03 g, N, N-dimethyl-4-aminopyridine 0.03 g were added to methylene chloride 27. After dissolving in 5 ml at room temperature, dicyclohexylcarbodiimide 0.9
0 g was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain the target compound 1.
40 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.90 (m, 6H), 1.20-
1.84 (m, 31H), 4.02 (t, 2H), 5.
18 (m, 1H), 7.00 (m, 2H), 7.13
(M, 2H), 7.39 (m, 1H), 7.46 (m,
1H), 7.57 (m, 2H), 8.00 (m, 1
H), 8.10 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2926,285
5,1732, 1614, 1433, 1285, 125
4,1133. Specific rotation [α] _D ²⁰ = -18.13 ° (C, 2.03
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0070]

(Equation 6)

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. The compound exhibited double hysteresis characteristics at 70 ° C.

(Example 7) ((R) -4'-octyloxy-3-fluoro-4-biphenylcarboxylic acid-4-
(1-Methylhexyloxycarbonyl) -3-fluorophenyl ester)

[0073]

[Chemical formula 22]

4'-octyloxy-3-fluoro-4
-Biphenylcarboxylic acid 1.50 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylhexyl ester 1.10 g, N, N-dimethyl-4-aminopyridine 0.03 g methylene chloride 30.9 ml In room temperature at room temperature and then dicyclohexylcarbodiimide 1.00
g was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to give the target compound 1.5.
0 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.87-0.91 (m, 6H), 1.30-
1.84 (m, 23H), 4.02 (t, 2H), 5.
18 (m, 1H), 7.00 (m, 2H), 7.13
(M, 2H), 7.40 (m, 1H), 7.47 (m,
1H), 7.57 (m, 2H), 8.01 (m, 1
H), 8.11 (m, 1H). IR spectrum (KBr method, cm ^-1 ): 2927,285
8,1731, 1614, 1431, 1287, 125
0,1134. Specific rotation [α] _D ²⁰ = -18.91 ° (C, 2.03
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0076]

(Equation 7)

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 90 ° C.

Example 8 ((R) -2- (4-decyloxy) phenyl-5-pyrimidinecarboxylic acid-4-
(1-Methylpentyloxycarbonyl) phenyl ester)

[0079]

[Chemical formula 23]

2- (4-decyloxy) phenyl-5-
Pyrimidinecarboxylic acid 1.40 g, (R) -4-hydroxybenzoic acid-1-methylpentyl ester 0.87
g, N, N-dimethyl-4-aminopyridine 0.03 g
Was dissolved in 28.0 ml of methylene chloride at room temperature, 0.90 g of dicyclohexylcarbodiimide was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain 1.30 g of the target compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.92 (m, 6H), 1.15
1.90 (m, 25H), 4.06 (t, 2H), 5.
17 (m, 1H), 7.01 (d, 2H), 7.33
(D, 2H), 8.51 (d, 2H), 9.40 (s,
2H). IR spectrum (KBr method, cm ^-1 ): 2926,173
2,1714,1583,1436,1273,121
3,1163,1093. Specific rotation [α] _D ²⁰ = -18.80 ° (C, 2.01
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0082]

[Equation 8]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 4 shows the optical response double hysteresis characteristic at 109 ° C. of the target compound. The compound shows a good double hysteresis characteristic.

(Example 9) ((R) -2- (4-decyloxy) phenyl-5-pyrimidinecarboxylic acid-4-
(1-Methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0085]

[Chemical formula 24]

2- (4-decyloxy) phenyl-5-
Pyrimidinecarboxylic acid 1.00 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylheptyl ester 0.75 g, N, N-dimethyl-4-aminopyridine 0.02 g in methylene chloride 21.0 ml. After dissolving at room temperature, dicyclohexylcarbodiimide 0.65 g
Was added and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to give the target compound 1.1.
0 g was obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.91 (m, 6H), 1.20-
1.85 (m, 29H), 4.06 (t, 2H), 5.
18 (m, 1H), 7.01 (d, 2H), 7.13
(D, 2H), 8.03 (m, 1H), 8.51 (d,
2H), 9.38 (s, 2H). IR spectrum (KBr method, cm ^-1 ): 2926,173
7,1708,1584,1435,1279,113
5. Specific rotation [α] _D ²⁰ = −19.07 ° (C, 2.06
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0088]

[Equation 9]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 5 shows the optical response double hysteresis characteristic of the target compound at 108 ° C. The compound shows a good double hysteresis characteristic.

Example 10 ((R) -4- (5-decyloxypyrimidin-2-yl) benzoic acid-4- (1-)
Methylpentyloxycarbonyl) phenyl ester)

[0091]

[Chemical 25]

4- (5-decyloxypyrimidine-2-
Yl) benzoic acid 1.40 g, (R) -4-hydroxybenzoic acid-1-methylpentyl ester 0.86 g, N,
After dissolving 0.02 g of N-dimethyl-4-aminopyridine in 35.1 ml of methylene chloride at room temperature, 0.90 g of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the precipitated solid matter was separated by filtration, and 3
% Aqueous solution of hydrochloric acid, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain 1.40 g of the target compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.94 (m, 6H), 1.20-
1.90 (m, 25H), 4.13 (t, 2H), 5.
17 (m, 1H), 7.32 (d, 2H), 8.12
(D, 2H), 8.28 (d, 2H), 8.50-8.
52 (m, 4H). IR spectrum (KBr method, cm ⁻¹ ): 2928,172
7, 1713, 1444, 1280. Specific rotation [α] _D ²⁰ = -18.68 ° (C, 2.05
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0094]

[Equation 10]

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. This compound showed a double hysteresis characteristic at 123 ° C.

Example 11 ((R) -4- (5-decyloxypyrimidin-2-yl) benzoic acid-4- (1-)
Methylheptyloxycarbonyl) phenyl ester)

[0097]

[Chemical formula 26]

4- (5-decyloxypyrimidine-2-
Yl) benzoic acid 1.40 g, (R) -4-hydroxybenzoic acid-1-methylheptyl ester 1.03 g, N,
After dissolving 0.03 g of N-dimethyl-4-aminopyridine in 30.0 ml of methylene chloride at room temperature, 0.92 g of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the precipitated solid matter was separated by filtration, and 3
% Aqueous solution of hydrochloric acid, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain 1.30 g of the target compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.90 (m, 6H), 1.20-
1.90 (m, 29H), 4.13 (t, 2H), 5.
17 (m, 1H), 7.32 (d, 2H), 8.13
(D, 2H), 8.28 (d, 2H), 8.51 (m,
4H). IR spectrum (KBr method, cm ^-1 ): 2926,285
5,1727,1713,1444,1280,123
1,1073. Specific rotation [α] _D ²⁰ = -21.14 ° (C, 2.00
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0100]

[Equation 11]

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 112 ° C.

Example 12 ((R) -4- (5-decyloxypyrimidin-2-yl) benzoic acid-4- (1-)
Methylpentyloxycarbonyl) -3-fluorophenyl ester)

[0103]

[Chemical 27]

4- (5-decyloxypyrimidine-2-
Yl) benzoic acid 1.40 g, (R) -4 hydroxy-2
-Fluorobenzoic acid-1-methylpentyl ester 0.
94 g, N, N-dimethyl-4-aminopyridine 0.0
After dissolving 3 g in 28.0 ml of methylene chloride at room temperature, 0.90 g of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain 1.50 g of the target compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.94 (m, 6H), 1.20-
1.90 (m, 25H), 4.13 (t, 2H), 5.
18 (m, 1H), 7.13 (m, 2H), 8.02
(M, 1H), 8.26 (m, 2H), 8.51 (m,
4H). IR spectrum (KBr method, cm ^-1 ): 2930,172
8, 1709, 1616, 1444, 1289, 105
9. Specific rotation [α] _D ²⁰ = -16.99 ° (C, 2.03
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0106]

[Equation 12]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound showed double hysteresis characteristics at 125 ° C.

(Example 13) ((R) -4- (5-decyloxypyrimidin-2-yl) benzoic acid 4- (1-methylheptyloxycarbonyl) -3-fluorophenyl ester)

[0109]

[Chemical 28]

4- (5-decyloxypyrimidine-2-
Yl) benzoic acid 1.10 g, (R) -4-hydroxy-
After dissolving 0.83 g of 2-fluorobenzoic acid-1-methylheptyl ester and 0.02 g of N, N-dimethyl-4-aminopyridine in 23.2 ml of methylene chloride at room temperature, 0.71 g of dicyclohexylcarbodiimide was added. The mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate.
After the desiccant was filtered off, the solvent was distilled off. The obtained product is purified by silica gel column chromatography and recrystallization with ethanol to give 1.30 g of the desired compound.
I got

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.90 (m, 6H), 1.20-
1.90 (m, 29H), 4.13 (t, 2H), 5.
18 (m, 1H), 7.13 (m, 2H), 8.01
(M, 1H), 8.26 (m, 2H), 8.51 (m,
4H). IR spectrum (KBr method, cm ⁻¹ ): 2928,172
9, 1615, 1444, 1289, 1244, 113
4. Specific rotation [α] _D ²⁰ = -19.09 ° (C, 2.01
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0112]

[Equation 13]

From this, it can be seen that the target compound is an antiferroelectric liquid crystal compound. This compound exhibited a double hysteresis characteristic at 118 ° C.

(Example 14) ((R) -4- (5-decylpyrimidin-2-yl) benzoic acid 4- (1-methylpentyloxycarbonyl) -3-fluorophenyl ester)

[0115]

[Chemical 29]

4- (5-decylpyrimidin-2-yl)
Benzoic acid 1.10 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylpentyl ester 0.84
g, N, N-dimethyl-4-aminopyridine 0.02 g
Was dissolved in 31.4 ml of methylene chloride at room temperature, 0.81 g of dicyclohexylcarbodiimide was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallized from ethanol to obtain 1.20 g of the objective compound.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.94 (m, 6H), 1.20-
1.80 (m, 25H), 2.66 (t, 2H), 5.
18 (m, 1H), 7.13 (m, 2H), 8.02
(M, 1H), 8.28 (m, 2H), 8.58 (m,
2H), 8.68 (s, 2H). IR spectrum (KBr method, cm ^-1 ): 2923,285
1,1735, 1713, 1436, 1295, 124
9,1134,1069. Specific rotation [α] _D ²⁰ = -16.63 ° (C, 1.99
0, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0118]

[Equation 14]

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 6 shows the optical response double hysteresis characteristic of the target compound at 86 ° C. The compound shows a good double hysteresis characteristic.

(Example 15) ((R) -2- (4-decanoyloxy) phenyl-5-pyrimidinecarboxylic acid-
4- (1-methylpentyloxycarbonyl) -3-fluorophenyl ester)

[0121]

Embedded image

2- (4-decanoyloxy) phenyl-
5-pyrimidinecarboxylic acid 1.20 g, (R) -4-hydroxy-2-fluorobenzoic acid-1-methylpentyl ester 0.75 g, N, N-dimethyl-4-aminopyridine 0.02 g were added to methylene chloride 22. After dissolving in 2 ml at room temperature, dicyclohexylcarbodiimide 0.7
2 g was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated solid matter was separated by filtration, washed with 3% hydrochloric acid aqueous solution, water and saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off. The obtained product was purified by silica gel column chromatography and recrystallization with ethanol to obtain the target compound 1.
15 g were obtained.

¹ H-NMR spectrum (CDCl ₃ , ppm
): 0.86-0.94 (m, 6H), 1.20-
1.82 (m, 25H), 2.59 (t, 2H), 5.
18 (m, 1H), 7.12-7.16 (m, 2H),
7.26 (m, 2H), 8.04 (m, 1H), 8.6
1 (m, 2H), 9.43 (s, 2H). IR spectrum (KBr method, cm ^-1 ): 2928,176
1,1740,1583,1431,1255,116
7,1136. Specific rotation [α] _D ²⁰ = -16.83 ° (C, 2.02
5, in CHCl _3). As a result of the measurement, the phase sequence of the target compound was as follows.

[0124]

(Equation 15)

From this, it is understood that the target compound is an antiferroelectric liquid crystal compound. Further, FIG. 7 shows the optical response double hysteresis characteristic of the target compound at 120 ° C. The compound shows a good double hysteresis characteristic.

(Example 16) (R) synthesized in Example 2
-4'-decyloxy-3-fluoro-4-biphenylcarboxylic acid-4- (1-methylheptyloxycarbonyl) -3-fluorophenyl ester and known antiferroelectric material represented by the following chemical structural formula (A) Sex compound MHPOB
C (AD Chandani et al., Jpn. J. App.
ly. Phys. , 27, L729 (1988))

[0127]

[Chemical 31]

[0128]

[Equation 16]

A composition mixed at a weight ratio of 1: 1 was prepared, and an optical response double hysteresis characteristic was measured. The phase sequence of the prepared composition was as follows as a result of the measurement.

[0130]

[Equation 17]

In FIG. 8, the optical response double hysteresis characteristic at 80 ° C. of the above composition is shown by a solid line, and the optical double hysteresis characteristic of the known compound represented by the formula (A) at 85 ° C. is shown by a broken line.
The composition of this example exhibits a better double hysteresis characteristic than the compound of the formula (A).

(Example 17) (R) synthesized in Example 9
2- (4-decyloxy) phenyl-5-pyrimidinecarboxylic acid 4- (1-methylheptyloxycarbonyl) -3-fluorophenyl ester and a known anti-reactive compound represented by the chemical structural formula (A) in Example 16 A composition in which a ferroelectric compound was mixed at a weight ratio of 1: 1 was prepared, and an optical response double hysteresis characteristic was measured. The phase sequence of the prepared composition was as follows as a result of the measurement.

[0133]

(Equation 18)

In FIG. 9, the optical response double hysteresis characteristic of the above composition at 83 ° C. is shown by a solid line, and the optical double hysteresis characteristic of the known compound represented by the formula (A) at 85 ° C. is shown by a broken line.
The composition of this example exhibits a better double hysteresis characteristic than the compound of the formula (A).

From Examples 16 and 17, it can be seen that the optically active compound of the present invention is useful as a composition.

[Brief description of drawings]

FIG. 1 is a graph schematically showing a relationship between an applied voltage and an amount of transmitted light in an antiferroelectric liquid crystal display device.

FIG. 2 is a graph showing the optical response double hysteresis characteristic of the target compound of Example 1 at 80 ° C.

FIG. 3 is a graph showing the optical response double hysteresis characteristic of the target compound of Example 2 at 90 ° C.

FIG. 4 is a graph showing optical response double hysteresis characteristics of the target compound of Example 8 at 109 ° C.

5 is a graph showing the optical response double hysteresis characteristic at 108 ° C. of the target compound of Example 9. FIG.

FIG. 6 is a graph showing the optical response double hysteresis characteristic of the target compound of Example 14 at 86 ° C.

FIG. 7 is a graph showing the optical response double hysteresis characteristic at 120 ° C. of the target compound of Example 15.

8 is a graph showing the optical response double hysteresis characteristic at 80 ° C. (solid line) of the composition of Example 16, and the optical response double hysteresis characteristic at 85 ° C. (broken line) of the known compound used in this example.

9 is a graph showing the optical response double hysteresis characteristic at 83 ° C. (solid line) of the composition of Example 17, and the optical double hysteresis characteristic at 85 ° C. (broken line) of the known compound used in this example.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kazuaki Esaka 14 Iwatani, Shimohakaku-cho, Nishio-shi, Aichi Japan Auto Parts Research Institute (72) Inventor Hitoshi Suenaga 5-41 Senmon, Itami-shi, Hyogo Empire Chemical Industry Co., Ltd.Itami Plant (72) Inventor Kazuaki Tabayashi 5-11 41 Senmon, Itami City, Hyogo Prefecture Imperial Chemical Industry Co., Ltd. Itami Plant

Claims (9)

[Claims] 1. An optically active compound represented by the following general formula (1): [In the formula (1), m and n are 6 ≦ m ≦ 14 and 3 ≦ n ≦, respectively.
Is an integer satisfying 10, X is any one of a single bond, O and COO, Y is H or F, and * represents an asymmetric carbon atom. ] 2. An optically active compound represented by the following general formula (2). Embedded image [In the formula (2), m and n are 6 ≦ m ≦ 14 and 3 ≦ n ≦, respectively.
Is an integer satisfying 10, X is a single bond, O or COO, and A is B is one of the following: , And * represents an asymmetric carbon atom]. 3. An antiferroelectric liquid crystal composition containing at least one optically active compound represented by the general formula (1) and at least one optically active compound represented by the general formula (2). 4. The optically active compound represented by the general formula (1) according to claim 1, wherein m and n are 7 ≦ m ≦ 12,4, respectively.
An integer satisfying ≦ n ≦ 8, X is either a single bond or O, and Y is H or F. 5. The optically active compound represented by the general formula (2) according to claim 2, wherein m and n are 7 ≦ m ≦ 12,4, respectively.
Is an integer satisfying ≦ n ≦ 8, X is a single bond, O and CO
Is one of O and A is One of which. 6. An antiferroelectric liquid crystal composition containing at least one of the optically active compounds shown in claims 4 and 5. 7. The optically active compound represented by the general formula (1) according to claim 1, wherein m and n are 7 ≦ m ≦ 12,4, respectively.
An integer that satisfies ≦ n ≦ 6, X = O, and Y is H or F. 8. The optically active compound represented by the general formula (2) according to claim 2, wherein m and n are 7 ≦ m ≦ 12,4, respectively.
An integer satisfying ≦ n ≦ 6, and X is either a single bond or O. 9. An antiferroelectric liquid crystal composition containing at least one of the optically active compounds shown in claims 7 and 8.