JPS63201147A - Liquid crystal compound and liquid crystal composition containing said compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is 1-16C alkyl or alkoxy; X is -O- or group shown by formula VIII; l and m are 1 or 2; n is 1-7; C* is asymmetric C). EXAMPLE:R-(-)-p-n-Decyloxybenzoic acid-p'-(2-methylpentyloxy)phenyl ester. USE:A component for liquid crystal composition. A liquid crystal compound which is useful for controlling liquid crystal state, is capable of showing chiral smectic C phase in a temperature range from low temperature to high temperature, is added to a liquid crystal composition to adjust temperature range and phase change state of the liquid crystal composition and is used for liquid crystal element. PREPARATION:An optically active alcohol shown by formula II is reacted with p-toluenesulfonic acid chloride shown by formula III in dried pyridine to form a compound shown by formula IV, which is reacted with a compound shown by formula V to give a compound shown by formula VI. Then this compound is reacted with a compound shown by formula VII, to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing the same.
The present invention relates to a liquid crystal compound derived from methylpentanol and a liquid crystal composition containing the same.

As a conventional liquid crystal element, for example, M-Shut (M,
5chadt) and double knee Helfrich (W, H
“Applied Physics Letters” written by e1frich
ers”) No. 18%, No. 4 (February 15, 1971)
“Voltage Dependent Optical Activities”, pp. 127-128
A Twisted Nematic Liquid Crystal” (Voltage Dependent Optica)
lActivity of a T+vis
ted NematicLiquid Crysta
Twisted nematic shown in
ted nematic) using liquid crystals are known. This TN liquid crystal has a problem in that crosstalk occurs during time division driving using a matrix electrode structure with high pixel density, so the number of pixels is limited.

Furthermore, its use as a display has been limited due to its slow electric field response and poor viewing angle characteristics.

Furthermore, a display element is known in which a switching element using a thin film transistor is connected to each pixel, and each pixel is switched. However, the process of forming the thin film transistor on the substrate is extremely complicated, and the display element has a large area. There are some problems that make it difficult to create.

To improve the drawbacks of conventional liquid crystal devices, the use of bistable liquid crystal devices is proposed by Clark (C1
ark) and Lagarwall (Japanese Unexamined Patent Publication No. 107216/1983,
(U.S. Pat. No. 4,367,924, etc.), chiral smectic C is generally used as a liquid crystal having bistability.
A strongly conductive liquid crystal having a phase (SmC'') or an H phase (SmH'') is used.

This strongly electrostatic liquid crystal has a very fast response speed due to its spontaneous polarization, and can also develop a bistable state with memory properties.Furthermore, it has excellent viewing angle characteristics, so it has a large capacity. It is expected to be used as a material for large-screen displays.

Until now, p-decyloxybenzylidene-p'-
Amino-2-methylbutylcinnamate (DOBAMB)
Several compounds have been studied, including Schiff base liquid crystal compounds represented by C), but stability, temperature range,
It cannot be said that the switching characteristics and the like are practically satisfactory.

long-term The present invention has been made in view of the above points.

That is, an object of the present invention is to provide a liquid crystal compound useful for controlling a liquid crystal state, a liquid crystal composition containing the same, and a liquid crystal element using the liquid crystal composition.

11 and 1 The present invention has been made to achieve the above-mentioned object, and has the general formula (I) [wherein R is an alkyl group or an alkoxy group having 1 to 16 carbon atoms, and X is 10- or -co-, L
%m is 1 or 2, ■ n is an integer from 1 to 7, CI represents an asymmetric carbon atom,
] The present invention provides a liquid crystalline compound represented by the following.

Further, the present invention provides the above-mentioned liquid crystal compound at least if
The present invention also provides a liquid crystal composition containing the ffis as a compounding component and a liquid crystal element using the liquid crystal composition.

``The method for producing the liquid crystalline compound represented by the formula (I) according to the present invention will be explained.

First, as a starting material, the following general formula (If) (where n
is 1 to 5, C1 represents an asymmetric carbon atom). This formula (I
The optically active alcohol represented by 1) is an optically active 2-
Using methylpentanoic acid as a raw material, according to the following process formulas (I) and (2), or the reaction of process formula (2) (-C
It can be easily synthesized by repeating H, -).

Process (I) ++Lt Process (2)! (In the process formula, y is an integer from 1 to 5) (C)12) y
CH2CH20H General formula (I1) (i.e.!!-1 to II-3)
A liquid crystalline compound represented by the general formula (I) can be obtained by using the optically active alcohol represented by the following reaction process formula (3).

Table 1 shows typical examples of the liquid crystalline compound represented by the general formula (I) of the present invention.

In the table, the symbols in the phase transition temperature column indicate the following phases.

Cryst, : crystal phase, ch, : cholesteric phase, Iso : iso-iron phase, SA: smectic A phase, Sc
! : chiral smectic C phase, S3: smectic phase other than sA, sc'' (unidentified).

In addition, the absolute configuration column in the table shows the absolute configuration of the optically active substance in formula (I), and (S) is 5inister.
type, (R) represents the Rectus type.

According to Table 1, the compound represented by general formula (I) has R%1
, m, n% By selecting By mixing them as components, it is possible to adjust the temperature range and phase change state of the liquid crystal composition.

Furthermore, the liquid crystal compound of formula (I) according to the present invention can be obtained from 2-methylbutanol (usually only the natural S type is available), which has been mainly used as an optically active group in ferroelectric liquid crystals. Unlike those in which the absolute configuration of the optically active substance is S-type or R-type can be freely selected. This is because optically active 2-methylpentanoic acid, which is a raw material for the synthesis of optically active alcohol represented by the general formula (I),
Special Application No. 1983-6311 (dated Satsuki 17, 1986)
As described in the specifications of , R type and S type can be selectively manufactured. This means that both optical isomers in which the helical twist direction of the SmC" phase or cholesteric phase is opposite can be freely obtained, and the helical pitch of the SmC" phase or cholesteric phase of the ferroelectric liquid crystal composition is It is effective for adjusting the

Further, the liquid crystal composition of the present invention contains at least one liquid crystal compound represented by the general formula (I) as a compounding component. For example, this liquid crystalline compound can be expressed by the following formula (I
) to (I4) can be used in combination with ferroelectric liquid crystals.

In such cases, the liquid crystal compound of the present invention represented by general formula (I) may be added to the resulting liquid crystal composition in an amount of 0.1 to
It is preferably used in a proportion of 99Ii by weight, particularly from 1 to 90% by weight.

Back' -COOCHz CHCt Hs 4.4'-7
Methylbutyl)ester 4'-(2-fluoropentyloxy)phenyl-4-octyloxybenzoate Also, by blending it with a smectic liquid crystal that is not chiral itself, as shown in the following formulas 1) to 5), ferroelectric properties can be obtained. A composition usable as a liquid crystal is obtained.

In this case, it is preferable to use the liquid crystalline compound of the present invention represented by general formula (I) in an amount of 0.1 to 99% by weight, particularly 1 to 90% by weight of the resulting liquid crystal composition.

4.4'-Decyloxyazoxybenzene Cryst-
4% Yakaj-N-1 ear 1go.

phenyl)pyrimidineCrrst-1?93di,u 5IIc 4(di'
]≧, 1 S-^ 21B” CIso.

2-(4'-octyloxyphenyl)-5-nonylpyrimidine Cr7st, 332! ;,, Sac
J% 5IA4 Iso.

4'-Pentyloxyphenyl-4-octyloxybenzoate Cryst, 58℃ - 84℃
-＾ 66℃ N 85℃ Lso.

--1--ri ------Kamo -m--ri -111-shi Here, the symbols indicate the following phases, respectively.

Cryst: crystalline phase, SsA: smectic A phase.

5IIB: Smectic B phase, 5LIC: Smectic C phase, N: Nematic phase, Iso:
Tokichi phase.

By the reaction steps shown in (I), (2), and (3) below, R(-) -p-n-decyloxybenzoic acid-p'-(2-methylpentyloxy) of the above formula Phenyl ester was produced.

(I) Production of R-(+)-2-methylpentanol Lithium aluminum hydride 1.49 g (39,2
mM) was suspended in dry ether 15+al and R-(-
)-2-methylpentanoic acid ([α]300-14.9°
(C-1, CHs 0H) 4.52g (39,0mM
) in 5IIll of dry ether at 0°C for 2
After 0 minutes of addition, the mixture was heated under reflux for 3 hours.

After the reaction was completed, distilled water 71111 was added at 0°C, and then 6
N sulfuric acid 30111 was added to decompose unreacted lithium aluminum hydride. After separating the aqueous layer and the ether layer, the aqueous layer was extracted twice with ether, and this ether layer was extracted with
% potassium carbonate aqueous solution. Add sodium sulfate and dry overnight. Nithyl was distilled off and purified by vacuum distillation to obtain 3.39 g of R-(+)-2-methylpentanol (
33.2mM) was obtained. Yield 85.1%, boiling point 90℃/
107 torr, [al “4+ 10.7” (C
m 1, ether).

(2) Production of R-(-)-p-(2-methylpentyloxy)phenol.

R-(+)-2-methylpentanol 1.02g (I0.0mM) obtained in (I) above, dried and lysine 2
．． 37g (30.0mM) was added and stirred at 0°C for 10 minutes. 2.11 g of P-toluenesulfonyl chloride (I1, 0mM) was added to this solution, and the temperature was kept at 0°C.
After the reaction was completed, the mixture was stirred at room temperature for 3 hours and then at room temperature for 3 hours. After the reaction was completed, 2M hydrochloric acid was added and the mixture was extracted twice with methylene chloride.

This extract was washed once with distilled water, and the distilled water was extracted three times with methylene chloride. This was added to the previously extracted methylene chloride solution, anhydrous sodium sulfate was added, and the mixture was dried overnight. Methylene chloride was distilled off, and 2.40 g of (-)-2-methylpentyl p-toluenesulfonic acid ester (9,
38mM) yield 93°8%, [α]2@,2
．． -2. 27° (C=1, CH.

C1,).

3+nl of 1-butanol was added to 2.30g (8.98mM) of (-)-2-methylpentyl p-toluenesulfonic acid ester obtained above and 1.98g (I8.0mM) of hydroquinone and stirred well. , add a solution in which 55 g (I3, 8 mM) of sodium hydroxide Q was previously dissolved in 7 1 of 1-butanol,
After the reaction was completed by heating under reflux for 6 hours, distilled water was added and the mixture was extracted twice with ether. This extract was washed once with distilled water,
This distilled water was extracted once with ether. This was added to the previously extracted ether solution, anhydrous sodium sulfate was added, and the mixture was dried overnight. Ether was distilled off, methylene chloride was added, and the mixture was filtered. The solvent of this filtrate was distilled off, and it was separated by TLC (preparative thin layer chromatography) using methylene chloride as a developing solution, and eluted with a solvent of methylene chloride: methanol concentration 4:1. (0.78 g (4.02 mM) of 2-methylpentyloxyphenol was obtained.

Yield 44.8%, [α]27.2-4.33° (C=1
, CHzCl,)- (:l) R-(-)-p-n-decyloxybenzoic acid-p'-(2-methylpentyloxy)phenyl ester.

sp-n-decyloxybenzoic acid 0.96g (3,45m
After heating and refluxing M) with thionyl chloride for 1 hour, unreacted thionyl chloride was distilled off to obtain an acid chloride.

Next, 0.78g of triethylenediamine (6,96mM
) was dissolved in dry benzene 71, potassium hydroxide was added, and the mixture was dried for about 2 hours. This solution and R obtained in (2) above
-(-) -p-(2-Methylpentyloxy)phenol 0.67g (3.45mM) was added to the above acid chloride under stirring, and after the dropwise addition was completed, the mixture was heated at 50°C for 1 hour.

To this, 0.14 g of 60% sodium hydride (3,5
0mM) washed with dry benzene was added, and the mixture was heated under reflux for 2 hours.

After the reaction was completed, 1M hydrochloric acid was added and extracted with benzene. Anhydrous sodium sulfate was added to this benzene solution, and it was dried overnight.

Benzene was distilled off, and R-(-)-p-decyloxybenzoic acid-p'-(2-methylpentyloxy) was separated by TLC using benzene as a developing solution and eluted with benzene.
0.96 g (2.11 mM) of phenyl ester was obtained.

This was recrystallized with 2 ml of pentane, and the coarse filtrate was also separated by TLC as above and then recrystallized, and these were combined to give the final target product (-)-p-decyloxybenzoic acid-p'-
(2-methylpentyloxy)phenyl ester o, 8
7g (t, 9zmM) was obtained. Yield 55.7%, [
α]26・'-3,49°(C!1, CH, ct2),
[α]27·'-5,843ri7° (C-1, CHt C1z).

By the reaction steps shown in (I) and (2) below, the above formula S
-(+)-p-n-octyloxybenzoic acid-p'-(
2-Methylpentyloxy)phenyl ester was produced.

(I) S-(+)-p-(2-methylpentyloxyphenol S-(-)-2-methyl-pentanol 1.53 g
(I5,0mM) ([a]”-9,8°(neat
3.54g (45.0mM) of dry pyridine was added to )), and the mixture was stirred at 0°C for 10 minutes. To this solution, 3.15 g (I6, 5 mM) of P-toluenesulfonyl chloride was added little by little, and after the addition was completed, the mixture was stirred at 5 to 10°C for 2 hours, and then stirred at 20°C for 1 hour. 12
m1 was added and extracted three times with methylene chloride. The organic layer was washed with 8 ml of water, and the aqueous layer was extracted twice with 5 ml of methylene chloride. The methylene chloride layer was combined with the organic layer, dried over anhydrous magnesium sulfate, and the methylene chloride was distilled off under reduced pressure to obtain 3.08 g of S-(+)-2-methylbenzene-p-toluenesulfonic acid ester (I2,0 mM). 1.9' (C-2,0% CH2Cl2) was obtained, yield 80.2%.

s-(+)-2-methylbenzene p-toluenesulfonic acid ester obtained above 3.08g (I2,0mM)
and 2.64g (24.0mM) of hydroquinone
- 3.71 g of butanol was added and stirred well. Add 0.72 g of sodium hydroxide (I8,
A solution of 0mM) dissolved in 15ml of 1-butanol was added, and the reaction solution was heated under reflux for 6 hours. After cooling to room temperature, 25μl of water was added, and the mixture was extracted three times with ether. The organic layer was washed with 20+1 portions of water and then dried over anhydrous magnesium sulfate. Distill the ether under reduced pressure and add 5 ml of methylene chloride.
was added, the insoluble solid was passed through a furnace, and methylene chloride was distilled off under reduced pressure to obtain 2.30 g of a crude product. Separate this with TLC,
S -(+) -p -(2-methylpentyloxy)
1.24 g (6.3 mM) of phenol was obtained. Yield 5
3.2%, [al”+5°1' (C=2.1, CH
2C12) -(2) Production of S-(+)-p-n-octyloxybenzoic acid-p-(2-methylpentyloxy)phenyl ester.

0C12 n-Ca) (400H--→n CaH+tO(FOC
Ip-octyloxybenzoic acid 500mg (2.0mM
) and 4 ml of thionyl chloride were heated under reflux for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure. Triethylenediamine 448B (4.0mM) was contained in the generated acid chloride.
A solution of 466 g (2°4mM) of (+) -p-(2-methylpentyloxy)phenol dissolved in 4ml of dry benzene was added, and the mixture was heated and stirred at 50°C for 1 hour. 6. The reaction mixture was cooled to room temperature. After that, 58-g (2°4mM) of sodium hydride suspended in 1+*l of dry benzene was added, and after heating and stirring at 50°C for 30 minutes,
The reaction mixture was heated under reflux for an hour, then cooled to room temperature, and 5.0 ml of IM-hydrochloric acid was added dropwise, followed by 5.0 ml of water.

The organic layer was separated, and the aqueous layer was extracted with benzene.Then, the benzene layer was combined with the organic layer, washed with IM-sodium carbonate aqueous solution, and dried over anhydrous magnesium sulfate.
Benzene was distilled off to obtain 0.84 g of a crude product. This was purified by TLC to obtain 0.54 g (I, 27 mM) of (+)-p-octyloxybenzoic acid-p-(2-methylpentyloxy)phenyl ester. This was further washed with hexane to obtain 0.34g (0.80mM) of S-(+)-p-octyloxybenzoic acid-p'-(2-methylpentyloxy)phenyl ester. Yield 40
．． 0%, [α]20+3.9° (C=2, CH2
C12)- R-(-)-p-n-dodecyloxybenzoic acid-p'-(4-methylhebutyloxy) of the above formula is obtained by the reaction steps shown in (I), (2), and (3) below. Phenyl ester was produced.

(I) Production of R(+)-4-methylheptatool R-(+)-2-methylpentanol 2.56g (2
5.95 g (75.3 mM) of dry pyridine
) and then stirred for 10 minutes at 0°C, 5.28g (27.6mM) of P-toluenesulfonyl chloride was added dropwise. After stirring at 0°C for 3 hours, the mixture was stirred at room temperature for 3 hours.

After the reaction was completed, 2N hydrochloric acid was added, and the mixture was extracted twice with methylene chloride.

This methylene chloride layer was washed once with distilled water, and this distilled water was extracted three times with methylene chloride, and added to the previously extracted methylene chloride solution. Add sodium sulfate and dry overnight. Methylene chloride was distilled off and P-1-luenesulfonic acid-
6.03g (23.6mM) of 2-methylpentyl was obtained. Yield 93°8%, [α] 27.2-2.26°
(C=1, CH.

c12) - then distilled ethanol 11.2111 (I95mM
) was added with 0.60 g (26.1 mM) of sodium metal and heated appropriately to dissolve the sodium metal. To this, 4.83 g (30,2+wl) of diethyl malonate was added dropwise, followed by the p-toluenesulfonic acid obtained above.
5.93 g (23.2 mM) of 2-methylpentyl was added dropwise, and the mixture was heated and refluxed at 90° C. for 244 hours. After the reaction was completed, ethanol was distilled off, and the mixture was extracted with ether three times. Ether was distilled off to obtain 2-methylpentylmalonic acid diethyl ester.

4.20g (75.0mM) of potassium hydroxide was dissolved in 2.1l of distilled water and 2.1l of methanol, and the previously prepared diethyl 2-methylpentylmalonic acid ester was added dropwise for 6 hours after the dropwise addition. The mixture was heated to reflux.

After the reaction was completed, 6 ml of distilled water was added, methanol was distilled off, 6N@acid 101 was added, and the mixture was heated at 120° C. for 6 hours.

After the reaction is complete, separate the aqueous layer and organic layer, and add 4N to the organic layer.
It was made alkaline by adding NaOH and washed once with ether. This aqueous layer was made acidic by adding concentrated hydrochloric acid, and extracted three times with ether. Add sodium sulfate and dry overnight. The ether was distilled off, purified by vacuum distillation, and R-(-)-
1.57 g (I0.9mM) of 4-methylheptanoic acid was obtained. Yield 47.0%, boiling point 85°C/3 torr.

[al”・’-o, 97° (C-1, MeOH).

Lithium aluminum hydride 0.39g (I0.3m
M) was suspended in 5 ml of dry ether and R-(-)-4
A solution of 1.47 g (I0, 2 mM) of -methylhebutanoic acid dissolved in 2 ml of dry ether was added dropwise at 0° C. over about 15 minutes. After the dropwise addition, the mixture was heated under reflux for 3 hours.

After the reaction is complete, add 2g + 1 of distilled water at 0°C, then add 6N
10 ml of sulfuric acid was added to decompose unreacted lithium hydride. After separating the aqueous layer and the ether layer, the aqueous layer was extracted twice with ether, and the ether layer was washed with a 10% aqueous potassium carbonate solution. Add sodium sulfate and dry overnight.

The ether was distilled off, purified by vacuum distillation, and R-(+)-
4-Methylheptatool 0.99g (7,62mM)
I got it. Yield 74.7%, boiling point 95°C/75 tor
r.

[α] 32・0±0° (C=0.5, Et, O).

(2) R-(-)-p-(4-methylhebutyloxy)
Production of phenol R-4-methylheptatool 0.65g (5゜0mM
) ([Q] "+0.49"" (neat)) was added with 1.188 (t! 5.0 mM) of dry pyridine and stirred at 0°C for 10 minutes. To this solution was added 1.05 g of p-toluenesulfonyl chloride. (5.5mM) was added little by little,
After the addition was completed, stir at 5 to 10°C for 2 hours, and then stir for 25 minutes.
4 ml of 2M hydrochloric acid was added to the 0 reaction solution which was stirred for 1 hour at °C, and the mixture was extracted three times with methylene chloride. The organic layer was washed with 5 liters of water, and the aqueous layer was extracted twice with methylene chloride. The methylene chloride layer was combined with the organic layer, dried over anhydrous magnesium sulfate, and the methylene chloride was distilled off under reduced pressure to obtain (-)-4-methylhebutyl-p-toluenesulfonic acid ester 1.4
2g (5.0mM) was obtained. Yield 100%, [α12
2-1. g° (C=2, CH2Cl.

).

1.5 ml of 1-butanol was added to 1.42 g (5.0 mM) of the obtained (-)-4-methylhebutyl-p-toluenesulfonic acid ester and 1.10 g (I 0.0 mM) of hydroquinone, and the mixture was stirred well. . Add 0.3g (7.5mM) of sodium hydroxide to this solution in advance.
A solution dissolved in 6 ml of butanol was added, and the reaction solution was heated under reflux for 6 hours. After cooling to room temperature, water 101 was added and extracted three times with ether. The organic layer was washed with 10+al of water and then dried over anhydrous magnesium sulfate. The ether was distilled off under reduced pressure, 5 ml of methylene chloride was added, the insoluble solid was passed through a furnace, and the methylene chloride was distilled off under reduced pressure to obtain a crude product of 1.2
9g was obtained. This was separated by TLC-)"p-(4-
Methylhebutyloxy)phenol 0.64g (2,
88mM) was obtained. Yield 57.6%, [α]', 2-
1. g° (C-2,0, CH*C1i)- (3) Production of R-(-)-p-n-dodecyloxybenzoic acid-p'-(4-methylhebutyloxy)phenyl ester.

υ p-dodecyloxybenzoic acid 0.74g (2゜4mM
) and 4.8 ml of thionyl chloride were heated under reflux for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure. Triethylenediamine 0.54g (4,
8mM) and (-)-p-(4-methylhebutyloxy)
A solution of 0.84 g (2.9 mmol) of phenol dissolved in 11 g of dry benzene was added, and the reaction solution was heated and stirred for 1 hour. After cooling the reaction mixture to room temperature, 701 g (2.9 mmol) of sodium hydride was dissolved in dry benzene. The suspension was added to 1 ml, heated and stirred at 50°C for 30 minutes, heated under reflux for 2 hours, and cooled to room temperature.
ml was added dropwise, followed by the addition of 61 ml of water.

The organic layer was separated, and the aqueous layer was extracted with benzene.The benzene layer was then combined with the organic layer, washed with IM-sodium carbonate aqueous solution, and dried over anhydrous magnesium sulfate.
Benzene was distilled off to obtain 1.29 g of a crude product. This was separated and purified using a silica gel column to obtain R-(-)-p-
0.98g (I, 9mM) of dodecyloxybenzoic acid-p-(4-methylhebutyloxy)phenyl ester was obtained. Further, this was recrystallized from isopropyl ether 11 to obtain 0.72 g (I, 41 mM) of a purified product. Yield 58.7%, [α]♂−0,9° (C!2, CH2
C1x) - By the reaction steps shown in the following (I) and (2), the above formula s -(+) -p-n-octyloxybenzoic acid-
P'-(4-methylhebutyloxy)phenyl ester was produced.

(I) Production of s-(+)-'p-(4-methylhebutyloxy)phenol.

S-(-)-4-methylheptatool 0.82g (6
, 31mM) ([al 26'±01 (C-1,
Et, O)) and 1.50 g of dry pyridine (I9,0mM
) and stirred at 0°C for 10 minutes. In this solution, p
-Toluenesulfonyl chloride 1.33g (6,96
After the reaction was completed, 2M hydrochloric acid was added and the mixture was extracted twice with methylene chloride. This extract was washed once with distilled water, and the distilled water was extracted three times with methylene chloride. This was added to the previously extracted methylene chloride solution, anhydrous sodium sulfate was added, and the mixture was dried overnight.

Methylene chloride was distilled off and (+)-4-methylheptyl P
-Toluenesulfonic acid ester 1.32g (4,65
mM) was obtained. Yield 73.7%.

[α]26・'+1.47''' (C proverb 1, CH2C1
2).

(+)-4-Methylhebutyl P-toluenesulfonic acid ester 1.22g (4.30mM) and hydroquinone 0.95g (8.64mM), 1-butanol 1.
5 ml of sodium hydroxide was added and stirred.
A solution dissolved in 6 ml of butanol was added, and the mixture was heated and refluxed for 6 hours. After completion of the reaction, distilled water was added and the mixture was extracted twice with ether. This extract was washed once with distilled water, and the distilled water was extracted once with ether. This was added to the previously extracted ether solution, anhydrous sodium sulfate was added, and the mixture was dried overnight. Ether was distilled off, methylene chloride was added, and the mixture was filtered.

The solvent of this ψ solution was distilled off, separated by TLC using methylene chloride as a developing solution, and eluted with a solvent of methylene chloride:methanol-4:1 to produce S-(+)-p-(4-methylhebutyloxy). Phenol 0.53g (2.39mM)
I got it.

Yield 55.6%, [α] "6+1.90' (C-
1, CH2at2).

(2) S-(+)-p-n-octyloxybenzoic acid-
Production of p'-(4-methylhebutyloxy)phenyl ester.

p-octyloxybenzoic acid o, 49g (I°96m
After heating and refluxing M) with 3.5 ml of thionyl chloride for 1 hour, unreacted thionyl chloride was distilled off to obtain an acid chloride.

Next, 0.44 g of triethylenediamine (3°ta
3mM) was dissolved in 3.5ml of dry benzene, potassium hydroxide was added, and the mixture was dried for about 2 hours. This solution and S
-(+)-p-(4-Methylhebutyloxy)phenol 0.43g (I, 94mM) was added dropwise to the above acid chloride under stirring, and after the dropwise addition was completed, the mixture was heated at 50°C for 1 hour. Add to this 0.08g of 60% sodium hydride (2
, OOmM) washed with dry benzene was added, and the mixture was heated under reflux for 2 hours.

After the reaction was completed, 1M hydrochloric acid was added and extracted with benzene. Anhydrous sodium sulfate was added to this benzene solution, and it was dried overnight.

Benzene was distilled off, separated by TLC using benzene as a developing solution, and eluted with benzene. ) was obtained. Yield 68.4%.

[α]21・'+0.69° (C 1, c H,
ct.

), [a] ””+2. 37 ° (C-1, C
HtJS C1i) - This was recrystallized with pentane 21, and the p liquid was also
After separation by TLC, it is recrystallized and combined to obtain the final target product, S-(+)-p-octyloxybenzoic acid-p.
-(4-Methylhebutyloxy)phenyl ester 0.
40g (0.88mM) was obtained. Yield 45.4% [
a] 32-4 +□, 71''' (C cod 1%CH,
CI, ), [α]2@・6+3.03° (C!1, C
H2C12)-ILI≧Uni In place of p-alkoxybenzoic acid and p-substituted phenol used in Examples 1 to 4, R1 shown in Table 1 above, respectively.
In the same manner as in Examples 1 to 4, except that a carboxylic acid giving m1n, a carboxylic acid giving m1n, X, and a p-substituted phenol giving m, n% A liquid crystalline compound of the invention was obtained.

The specific optical rotation and phase transition temperature characteristic data of the product are also shown in Table 1 above.

Liquid crystal compound [R-(-)-p-n] prepared in Example 1
-Decyloxybenzoic acid-p-(2-methylpentyloxy)phenyl ester] was prepared as the following liquid crystal composition.

The obtained liquid crystal composition exhibited an SmC'' phase from 40°C to 22°C during the cooling process.

ITO (Indium Tln 0xi) is used as a 1L electrode.
de) A liquid crystal element with a liquid crystal layer thickness of 2 μm was prepared by sandwiching the liquid crystal composition prepared in Example 11 between a pair of electrode substrates on which the polyimide film covering Ili had been subjected to a rubbing treatment. A monodomain SmC phase was obtained. Drive voltage ±15v1 pulse width 300 at 30℃
When driven at μsec, a good switching state with a contrast of 15 was obtained.

Claims (1)

[Claims] 1. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (I) [Here, R is an alkyl group or an alkoxy group having 1 to 16 carbon atoms, and X is - Indicates O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. l, m are 1 or 2, and n
is an integer from 1 to 7, and C^* represents an asymmetric carbon atom. ] A liquid crystalline compound represented by: 2. In the formula (I) described in claim 1,
A liquid crystal compound characterized in that the absolute configuration of the optically active substance is R type. 3. In the formula (I) described in claim 1,
A liquid crystal compound characterized in that the absolute configuration of the optically active substance is S type. 4. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [Here, R is an alkyl group or alkoxy group having 1 to 16 carbon atoms, and X is -O- or ▲Numerical formula, There are chemical formulas, tables, etc. Showing ▼. l, m are 1 or 2, and n
is an integer from 1 to 7, and C^* represents an asymmetric carbon atom. ] A liquid crystal composition comprising at least one liquid crystal compound represented by the following. 5. General formula (I) below ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [Here, R is an alkyl group or alkoxy group having 1 to 16 carbon atoms, and X is -O- or ▲Numerical formula, There are chemical formulas, tables, etc. Showing ▼. l, m are 1 or 2, and n
is an integer from 1 to 7, and C^* represents an asymmetric carbon atom. ] A liquid crystal element characterized by using a liquid crystal composition containing at least one liquid crystal compound represented by the following.