JPS6360951A - Optically active liquid crystal compound and liquid crystal composition containing same - Google Patents

Abstract

NEW MATERIAL:The optically active compound of formula I (R is 1-18C alkyl; C* is asymmetric C; R<1> is 4-18C alkyl or alkoxy; X is -CH2-CH2- or -CH=CH-; Z is O or S; n and l are 0 or 1; m is 1-8). EXAMPLE:3-(p-n-Decyloxyphenyl)propionic acid 4'-(2-ethoxypropoxy)-phenyl ester. USE:A component of a liquid crystal composition. It is a liquid crystal compound useful for the control of liquid crystal state and effective in preventing the development of reverse domain in a TN-type cell by the addition to a nematic liquid crystal. Addition of the compound to a nematic liquid crystal or chiral nematic liquid crystal gives a chiral nematic liquid crystal which can be used as a phase-transition type or White-Taylor-type quest-host liquid crystal element. PREPARATION:The compound of formula I can be produced e.g. by reacting the compound of formula II with the acid chloride of formula III, converting the resultant compound of formula IV into the compound of formula V and reacting the product with the compound of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal compound, a liquid crystal composition containing the same, and a liquid crystal element using the liquid crystal composition.

12.1 As a conventional liquid crystal element, for example, M-Shut (M,
5chadt) and W Helfrich (He, He)
"Appliecf Phys, Letters Vol. 18, No. 4"
icsLetters”, Vol. 18. N
o, 4) (19?1.2.15), P.

127~! 28 “Voltage-Dependent Optical Behavior of Twisted Nematic Liquid Crystals”
0pticalActivit7 of a Tw
isted Ne5atic Liquid Cr7s
A device using a TN (twisted nematic) liquid crystal described and developed in ``Tal'' is known.However, this TN liquid crystal has a matrix electrode structure with a raised pixel structure. The number of pixels per pixel was limited due to the problem of crosstalk, and its use as a display was limited due to slow electric field response and poor viewing angle characteristics.

Furthermore, a display element is known in which a switching element using an FI 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 requires a large area. There is a problem that it is difficult to create the device.

To improve the drawbacks of conventional liquid crystal devices, the use of bistable liquid crystal devices has been proposed by Clark (C
1ark) and Lager (11) (Japanese Unexamined Patent Publication No. 56-107218, U.S. Pat. No. 4,387,924, etc.), liquid crystals having bistability generally include chiral smectic C phase ( A ferroelectric liquid crystal having a SmC") or an H phase (SmH") is used.

This ferroelectric liquid crystal has spontaneous polarization, so it has a very fast response speed, and can also develop a bistable state with memory properties.It also has excellent viewing angle characteristics, so it can be used for large-capacity, large-screen displays. It is suitable as

i and 2 yu The decision to not issue a report in January was made in consideration of the above points.

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.

&jLΩ''L In other words, the present invention is based on the general formula (I) (wherein R represents an alkyl group having 1 to 18 carbon atoms (
1 represents an asymmetric carbon atom l (l represents an alkyl group or alkoxyf having 4 to 18 carbon atoms, (X represents -CH
2-CH,- or -CH=CH-, Z represents 10- or -S-, n represents O or l, cross represents O or 1, m represents 1 to 8) The present invention provides an optically active liquid crystalline compound as shown in FIG.

The present invention also provides a liquid crystal composition containing at least one of the above-mentioned optically active liquid crystal compounds as a compounding component, and a liquid crystal element using the liquid crystal composition.

f1,? f A method for producing the liquid crystal compound of formula (I) according to the present invention will be explained.

First, as a starting material, the following general formula ([[) (where R
represents alkylnoS having 1 to 18 carbon atoms, C'' represents an asymmetric carbon atom, 0m represents 1 to 8, fL represents 0 or 1, and an optically active alcohol represented by the formula (!) is used.
The optically active alcohol represented by I) has the general formula (m) (where Ro is a lower alkyl group, C8 is an asymmetric carbon atom, and k is 0 or 1, and when the sentence is 0, k is 0
or l, and when the sentence is 1, it is O. ), specifically, 2-hydroxypropionic acid alkyl ester, 3-hydroxyacetic acid alkyl ester, and 3-hydroxy-2=methylpropionic acid alkyl ester, the following reaction process formulas (1) and (2) are carried out. Therefore, it can be easily synthesized by repeating the process formula (2).

! ”! −Ω work Hs CH.

CH.

tree q -ya tree fall -1-shi tree marriage
Kibata: RI in the above reaction formula can be selected from a wide range of carbon numbers, and specifically includes iodobutane, iodopentane, iodohexane, iodohebutane, iodooctane, iodononane, iododecane, iodoundecane, iododecane, Iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane.

Linear saturated hydrocarbon iodides such as iodoheptadecane, iodooctadecane, iodononadecane, iodoeicosane; branched saturated hydrogens such as 2-iodobutane, ■-iodo-2-methylpropane, l-iodo-3-methylbutane, etc. Iodide; iodobenzyl, iodophenacyl,
Cyclic unsaturated IR hydrogen iodides such as 3-iodo-1-cyclohexene: iodocyclopentane, iodocyclohexane, 1-iodo-3-methylcyclohexane.

There are cyclic saturated hydrocarbon iodides such as iodocyclohebutane and iodocyclooctane.

A typical synthesis example of the optically active alcohol represented by the formula ('+1) is shown below.

Synthesis of L 2-butoxypropanol (crossing=0, m=1.
R=n-C4He-)r-=(+)-31.5 g of ethyl lactate and 107.3 g of l-iodobutane are mixed into a four-eye flask, and newly synthesized AgzO is added over 2 hours.

After leaving at room temperature for 15 hours, add 200+Jj of ether to 6
After dilution and filtration, the ether is distilled off. The remaining amount is 5
After washing with 26KOH aqueous solution, anhydrous Na
Dry at 25O, vacuum distillation, 110℃/54m
When the mHg fraction was collected, 23 g of (=)-ethyl-2-
Butoxypropionate is obtained. Rotation 24' Luminous intensity [α - 73°LiA ACH, 2.0g was added to roomQ ether and 3
After stirring for hours, 12.7 g of (-)-ethyl-2-butoxypropione) was added dropwise.

Continue stirring for 15 minutes after the addition is complete. After that, add 50 m of wood and 50 m of 6H2SO4 aqueous solution. Separate the ether layer and dry over MgSO4. 't
The ether is distilled off using iA. Yield: 7.4 min. Synthesis of 3-pentyloxybutanol (text = 0, m = 2
, R=n-C5H11-) (R) -(-) -92゜1 g of methyl acetate and 389 g of pentyl iodide were added to the flask, and N2
Mixed under air flow. Add 271g of newly synthesized Ag2O and stir at 60-65℃ for 26 hours to roughly form Ag2O.
54.2 g was added and stirred at 60-65° for 58 hours.

After -fi filtration, the filtrate was thoroughly washed with ether, the ether of the p liquid was distilled off, and then distilled under reduced pressure.
Collecting the 59-layer Hg fraction yields 64.6 g of methyl 3
-Pentyloxybutyrate was obtained.

Next, add 9.4 g of LiA H, 31 OI 11 love ether, and add 63.6 g of methyl 3-pentyloxybutylene.
A 61 mM solution of 10 g of ether was added dropwise at 10° C. or lower over 2 hours. After the completion of the dropwise addition, the mixture was stirred at 20 to 25° C. for 2.5 hours, and then left to stand for 15 hours.

Thereafter, the mixture was acidified with an aqueous hydrochloric acid solution p)11) and extracted with ether. The ether layer was dried over water, 5% NaHCo, aqueous solution, and 1 Mg5O in water. 1N distillation under reduced pressure, 127~b/50 mmHg
When the W portion was collected, 34.2 g of 3-pentyloxybutanol was obtained.

IR (cm"): 3360.2970~2870.1370°1090°Salmon" Synthesis of 3-ethyloxy-2-methylpropanol (2
=1, m=1. R=C2Hs )(R) −(−)
Methyl -3-hydroxy-2-methylpropionate 1
Add 00g and 331g of ethyl iodide to the flask, and add N2
Mixed under air flow. 294 g of newly synthesized Agz was added and stirred at 60-65°C for 20 hours. After filtration, the filtrate was washed with ether, and the ether in the p liquid was distilled off.
Reduction If: Stay at -110°C/150mm
87 g of methyl 3-ethyloxy-2-methylpropionate was obtained as a Hg fraction.

Next, 18.5 g of LiA H4 was added to 610 m of ether, and a solution of 87 g of methyl 3-ethyloxy-2-methylpropionate in 122 mQ of ether was added dropwise at a temperature below 10"C over 6 hours. 2 in C.
After stirring for 5 hours, the mixture was left at room temperature for 15 hours. after that,
In 5% aqueous hydrochloric acid solution.

The mixture was acidified and extracted with ether. Add ether layer to water, 5%
Wash with Na HCO3 aqueous solution and water in order, M g SO
It was dried at a. After distilling off the ether, distillation was carried out under reduced pressure to give 110
-b 39 g of 3-ethyloxy-2-methylpropanol was obtained.

'IR (cm-1): 3380.2980~2870.1380, ttto,
1040゜Salmon' 4-n-octyloxypentanol (cross=0, m=3
, R= n CB H17) L -(+)-ethyl lactate 98 g, lactyl iodide 380 g and silver oxide 245
g was added thereto, and the mixture was stirred at 60°C for 16 hours. After filtering the insoluble matter, distill it under reduced pressure.

7 g of ethyl 2-octyloxypropionate was obtained as a fraction at 130° C./3 mmHg.

Next, in the diethyl ether 250 ■ sentence, LiA1H4
After adding 7.5 g and stirring for a while, the above ester body 56
A solution of 50 g of diethyl ether was added dropwise over 2 hours at 5°C or below, and after the dropwise addition, the solution was stirred in the chamber for 2 hours.
After the 0 reaction, which was left for 5 hours, 5% hydrochloric acid was added for 30 seconds.
The mixture was further acidified with 6N hydrochloric acid (pH to 1) and extracted with ether.

After washing with water, it was dried and smoked, and the solvent was distilled off. To decompression! 711/
39.5 g of 2-year-old cutyloxypropanol was obtained as a 111 g fraction at +107° C./3 ml.

Next, 230 mQ of pyridine was added to 70 g of the above alcohol, and while stirring, 85 g of tosyl chloride was added to 70 g of the alcohol at 10° C.
Added over 0 minutes. After stirring at this temperature for 15 minutes, the temperature was raised and the mixture was stirred at 20 to 24°C for 3.5 hours. After pouring into cold water, it was extracted with benzene, washed with 5% acid and water in that order, and dried.

Benzene was distilled off and (2-octyloxypropyl)p-
127 g of toluenesulfonate was obtained.

26.7 g of 95% sodium ethoxide was added to a 220-mL ethanol solution, and 73.1 g of 98% diethyl malonate was added dropwise at 36 to 38° over 50 minutes while stirring. After further stirring for 30 minutes, 127 g of the above tosylate compound was added dropwise at 36 to 38°C over 1 hour. 15 more
After stirring for a minute, the temperature was raised.

After the reaction was refluxed for 18 hours, Mizuki was injected, extracted with benzene, washed with water, and then dried.

The solvent was distilled off to obtain 149 g of ethyl 4-year-old ctyloxy-2-ethoxycarbonylvalerate.

Next, 88.5 g of 85% KOH was dissolved in 90 ml of water, and 149 g of the above ester compound was added dropwise at 20 to 25° C. over 50 minutes. After stirring for 30 minutes, the mixture was refluxed for 2 hours. After cooling, 1
While keeping the temperature below 5°C, 153 g of concentrated sulfuric acid was dissolved in 196 aM of water, and this was added dropwise over 1 hour. After stirring for 30 minutes, the mixture was allowed to flow for 3 hours. After cooling to room temperature, benzene oil was extracted.

Wash the benzene layer with 5'36 N a OH aqueous solution,
added to the aqueous layer. 6Nl water layer! ! acidic (p)I'l
), extracted with benzene, washed with water, and dried with anhydrous MgSo. The solvent was distilled off to give 4-octyloxyvaleric acid 54
I got g.

Add 110 g of LiA to 210 mu of dry ether, and while stirring, add 70 mu of ether containing 154 g of the above 1% carvone.
The solution was added dropwise over 70 minutes while being kept at 2 to 6°C, and then the temperature was raised to 23°C and stirred for 3 hours. After 12 hours of release, 5% 1'! ! Add acid while keeping the temperature below 15°C, acidify with hydrochloric acid, extract with ether, add water and 5% Na
It was washed with an OH aqueous solution and then with water, and dried with anhydrous Mg5O.

The solvent was distilled off, then distilled under reduced pressure at 150°C (75 mm)
10 g of (S)-4-octyloxypentanol was obtained as an Ig fraction.

I R (cm-') 3360.2970-2860.1460.1370.
1340.1080° An optically active liquid crystalline compound represented by the general formula (I) can be obtained using the optically active alcohol represented by the general formula (■) and according to the reaction scheme shown below.

The liquid crystal composition of the present invention is represented by the above general formula (1). It contains at least one optically active liquid crystal compound as a compounding component.

Among the above compositions, those containing ferroelectric liquid crystals as represented by the following formulas (1) to (13) can increase spontaneous polarization and further reduce viscosity. In such a case, the optically active liquid crystal compound of the present invention represented by the general formula (I) is preferably used in a proportion of 0.1 to 99% by weight of the resulting liquid crystal composition. %, particularly 1 to 90% by weight.

phenyl ester phenyl ester Cryst, -1 → SmA -1 → Iso.

SaCf to 16, /43.5 (3) CF (.

C1゜H2N 0 +COO (filter OCH=CHCt
Hs4-decylleoxybenzou, fragrant acid 4'-(2-methylbutyloxy)phenyl ester 44 50 fli5Cry
st, ->S! fJ" -1→ SmA--La Iso
.

(4) CH.

phenyl ester 49.5 63 C “Mast, -1 → 5IIIA -C Lso.

SmC"/48 phenyl ester Monomethylbutylcinnamate (DOBAMBC) CH.

■ COOCH2CHC2Hs 4.4'-7
methylbutyl) ester octyloxybiphenyl-4
-Carboxylate biphenyl-4'-carboxylate biphenyl- It can also be used as a ferroelectric liquid crystal by blending it with a smectyl liquid crystal, which itself is not chiral, as shown in the following formulas 1) to 5). A composition is obtained.

In this case, the liquid crystal composition from which the optically active liquid crystal compound of the present invention represented by general formula (I) can be obtained is 0, 1 to 99
It is preferable to use 1%, especially 1.0 to 90 nails h1%.

' cs Htyoicoo-@-ocs H,.

4.4'-7' Anxyhenzene CrysL
・77”C, SmC times J-N 41so・C6HuO
(Layer) 00CsH.

() Curse CQ HI7 C9H+52-(4'-
octyloxyphenyl)-5-nonylpyrimidine Cr
ypt, 33”CSmCGO”C frost A 75”C
! So.

4'-Pentyloxyphenyl-4-octyl ethylbenzoate Cryst, 58°C SmC84°C
Sa+A 6G℃ N 85℃ Iso.

−111−1ri −−−−−−〉−−ri
-1111=shi Here, the symbols indicate the following phases, respectively.

Crystal: Crystal phase, SmA:
Smectic A phase.

SmB: smectic B phase, SmC: smectic C phase, N: nematic phase, [so,: isotropic phase.

Further, the optically active liquid crystal compound of the above general formula (I) is 3
By adding to nematic liquid crystal.

This is effective in preventing the occurrence of reverse domains in TN type cells.

In this case, 1 of the liquid crystal composition obtained by adding the optically active liquid crystal compound of formula (I) to the nematic liquid crystal.
．． It is preferable to use the optically active liquid crystalline compound of formula (I) in a proportion of 0.01 to 50% by weight.

In addition, by adding it to a non-machined liquid crystal or a chiral nematic liquid crystal, it can be used as a chiral nematic liquid crystal and as a liquid crystal composition in a phase change type liquid crystal element or a white tiller type guest-host type liquid crystal element. .

Figure 1 is for explaining the operation of ferroelectric liquid crystal.

This is a schematic drawing of an example of a cell. 11a and ll
b is I n203.3 n02 or I
A substrate (glass plate) coated with a transparent electrode made of a thin film of T O (Indium-Tin Oxide) or the like, between which a liquid crystal molecular layer 12 is oriented perpendicularly to the glass surface and has an Smc" phase or an SmH" phase. There are 11 LCD screens. A thick line L3 represents a liquid crystal molecule, and this liquid crystal molecule 13 has a dipole moment (P) 14 in a direction perpendicular to the molecule. No, (board 2
When a pressure of 1 or higher than a certain threshold is applied between the electrodes 1 and llb, the helical structure of the liquid crystal molecules 13 is unraveled, and the liquid crystal molecules 13 are aligned so that all the dipole moments (P) 14 are directed in the direction of the electric field. You can change direction. The liquid crystal molecules 13 have an elongated shape and exhibit refractive index anisotropy in the long axis direction and the short axis direction. Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, depending on the voltage applied polarity, It is easily understood that this results in a liquid crystal optical modulation element whose optical properties change.

The thickness of the liquid crystal cell preferably used in the optical modulation element of the present invention can be made sufficiently thin (for example, less than 1000 yen).As the liquid crystal layer becomes thinner in this way, as shown in FIG. Even when no electric field is applied, the helical structure of the liquid crystal molecules unwinds, and its dipole moment (Pa or Pb) is directed downward (24a) or downward (24b).
take either of the following states. In such a cell, an electric field Ea or Eb of different polarity above a certain threshold value is applied as shown in FIG.
is applied by the voltage applying means 21a and 21b, the dipole moment changes direction to upward direction 24a or downward direction 24b corresponding to the electric field vector of electric field Ea or Eb, and accordingly, the liquid crystal molecules are in the first stable state, g 23 a or the second stable state 23b.

As mentioned earlier, there are two advantages to using such ferroelectricity as an optical modulation element.

That: J′Sl has an extremely fast response speed,
The second is that the alignment of liquid crystal molecules has bistability a
: fS2 point is 1 For example, to further explain with reference to FIG. 2, when the electric field Ea is applied, the liquid crystal molecules enter the first stable state 99
23 &, and this state is stable even when the electric field is turned off. When an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented to the second stable state 23b and change their orientation, but they remain in this state even if the electric field is increased by νJ. Further, as long as the applied electric field Ea or Eb does not exceed a certain threshold value, the previous orientation state is maintained. In order to effectively realize such fast response speed and bistability, it is preferable for the cell to have as much r'rJ as possible;
is suitable.

Next, specific examples of driving methods for ferroelectric liquid crystals are shown in Figures 3 to 5I.
This will be explained using A.

FIG. 3 is a schematic diagram of a cell 31 having a matrix electrode structure in which a ferroelectric liquid crystal compound (not shown) is sandwiched between. 32 is a scanning electrode group, and 33 is a signal electrode group. First, a case will be described in which scan electrode S is selected. 'A 4 IN (a) and i4 figure (b) are scanning signals, which are the electrical signals applied to the selected scanning electrode SL and the other scanning electrodes (unselected scanning electrodes) s, , Ss, It shows an electric signal applied to Sl... FIG. 4(C) and FIG. 4(d) show information signals from selected signal electrodes I1. I3. I
s and the electric signals given to the unselected signal electrodes If and I4.

In FIGS. 4 and 5, the horizontal axis represents time and the vertical axis represents voltage. For example, when displaying a moving image, the scanning electrode group 32 is sequentially moved.

Selected periodically. Now, the threshold voltage for providing the first stable state of the liquid crystal cell having bistability for a predetermined pressure application time L1 or t2 is set as -v th,
The I21 value voltage to give a stable state of 2 is +vth2
Then, the electrode signal applied to the selected scanning electrode 32 (Sl) is 2V at phase (time) 11 and -2V at phase (time) t2, as shown in FIG. 4(a). It is an alternating voltage like that. When electrical signals having multiple phase intervals with mutually different voltages are applied to the scanning electrodes selected in this way, the difference between the first or second stable state of the liquid crystal corresponding to the optical "dark" or "bright" state is generated. The important effect is that the state change can be caused quickly.

On the other hand, the other scanning electrodes S2 to S,... are in a grounded state as shown in FIG. 4(b), and receive the electrical signal O.
It is. Also, the selected signal type JfflI+,
The electrical signals given to I3 and I5 are shown in Figure 4 (C
), the signal electrodes I2.1. The electrical signal received by IP is <-V as shown in FIG. 4(d).

In the above, each rice transplant is set to a desired i11'i that satisfies the following relationship.

v<vth2<3v -3v(-vth, <-V Among the pixels when such an electric signal is applied, for example, the voltage waveforms applied to pixels A and B in FIG. (L) and (b), i.e., FIG.
As is clear from a) and (b), a voltage of 3v exceeding the darkness value v th2 is applied to the pixel A on the selected scanning line at phase t2. Furthermore, in the case of pixel B existing on the same scanning line, the phase is 1. At , a voltage of -3V exceeding the rice uue -v th is applied. Therefore, I:! ! Depending on whether or not a signal electrode is selected on the selected scanning electrode line, if selected, the liquid crystal molecules are aligned in the first stable state; if not selected, the liquid crystal molecules are aligned in the second stable state. Align the orientation to a stable state.

On the other hand, as shown in Fig. 5(C) and (d), in the unselected scanning line -H, the voltage applied to all pixels is V or 1, and both of them are agonizing (+Q exceeding the main voltage). Therefore, the liquid crystal molecules in each pixel other than those on the selected scanning line maintain the orientation corresponding to the state of signal 1) when scanned last time without changing the orientation state. That is, when a scanning electrode is selected, the signal is aged for one life, and the signal state can be maintained until the next selection after one frame is completed. Therefore, even if the number of scanning electrodes increases.

The actual duty ratio does not change, and there is no reduction in contrast at all.

Next, let us consider the problems that may actually occur when the device is driven as a display device.

In FIG. 3, scanning electrodes 5t-S, . . . and signal electrodes I
, ~I, . . . , the pixels shown in the shaded areas correspond to the "bright" state, and the pixels shown in white correspond to the "dark" state. Now, if you pay attention to the display above the signal electrode in Figure 3.

The pixel (A) corresponding to the scan electrode SI is in a "bright" state, and all other pixels (B) are in a "dark" state! & is. As an example of the driving method in this case, FIG. 6 shows a time-series representation of the scanning signal, the information signal applied to the signal electrode I, and the voltage applied to the pixel A.

For example, when driving as shown in Fig. 6, the scanning signal S
, is scanned for one hour [2, pixel A has I!
Since a voltage of 3V exceeding one value Vth is applied, one pixel A is in a stable state in one direction, that is, "bright", regardless of the previous history.
Transition to the state (Swee 2chi), then S2 to S,
While the image is being scanned, a voltage of <-V continues to be applied as shown in Figure 6, but since this does not exceed the threshold value -vthl, pixel A should be able to maintain its "bright" state. but,
In reality, when displaying information in which one signal (corresponding to "dark" in this case) is continuously given on one signal electrode, the number of scanning lines is extremely large and high-speed driving is required. However, by using the above-mentioned specific liquid crystal compound or a liquid crystal composition containing the same, such a reversal phenomenon can be completely prevented.

Furthermore, in the present invention, in order to prevent the above-mentioned reversal phenomenon, it is preferable to provide an insulating film made of an insulating material on at least one of the opposing electrodes constituting the liquid crystal cell.

The insulating material used in this case is not particularly limited, but silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide 1m hydrogen nitride, hydrogen Inorganic insulating materials such as boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and magnesium fluoride, or polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyvaraxylene, polyester, Organic insulating materials such as polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin, and photoresist resin are used as the insulating film. These IT! ! The thickness of the membrane is preferably 5000 Å or less, preferably 100 to 3000, particularly 500 to 3000.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Synthesis of JLIL 4-n-decyloxycinnamic acid-4'-(2-ethoxypropoxy)phenyl ester (Step 1) 4
-(2-ethoxypropoxy)phenol 140+tu of dry pyridine and 24 g of 2-ethoxypropanol were added to a flask, and while stirring under water cooling, 52.8 g of P-toluenesulfonyl chloride was added little by little. After the addition, the mixture was stirred at 25° C. for 5 hours and reacted overnight, then poured into cold water and extracted with benzene. After washing with water and drying, the solvent was distilled off to obtain 55.5 g of oily (2-ethoxypropyl) p-toluenesulfonate.

Next, 35.5 g of hydroquinone, 85% KOH14,8
g, methanol 60mM, and ethanol 310ml were added and stirred. 55.5g of sulfone)
The mixture was added dropwise at 0°C over 1 hour. Then the temperature was raised to 65°C.
The mixture was stirred for 2 hours and then for 8 hours under reflux. The mixture was cooled to room temperature, poured into cold water, extracted with hexane, washed with water, dried, and the hexane was distilled off to obtain 26.5 g of a crude product. This was recrystallized from hexane to obtain 13.7 [4-(2-ethoxypropoxy)phenol].

IR (c score-1) 3350.2960-2870, 1510.1450.
1230.1100° (Step 2) 4-n-decyloxycinnamate M -4'-(
2-ethoxypropoxy) phenyl ester 4-n-decyloxycinnamic acid2. Og and 10 ml of thionyl chloride were heated under reflux for 3.5 hours, excess thionyl chloride was distilled off under reduced pressure, and 10aM of toluene was added to form a solution. 4- (2
- 1.3 g of (ethoxypropoxy)phenol was dissolved in 5 ml of pyridine, and the toluene solution of 4-n-decyloxycinnamate acid chloride prepared above was added dropwise over 25 minutes at a reaction temperature of 0 to 2°C. The mixture was further stirred at room temperature overnight.

The reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was extracted with 6NI! ! Method fi+ was performed sequentially using acid, water, 2N aqueous sodium hydroxide solution, and water. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was chromatographed on silica gel (developing solvent: n-hexane/
Purified with ethyl acetate (10/2). Furthermore, it was recrystallized with ethanol and treated with activated carbon to obtain 2,881 g of 4-n-decyloxycinnamate S-4'-(2-ethoxypropoxy)phenyl ester.

The following IR data and phase transition temperature were obtained for the product.

IR (c layer-1): 3450.2925.2850. 1730°1638
．． 1608.1508.1318.1260.1144
, 238° (Sm3: SmC'', smectic phase other than SmA (unidentified)) The following compound is synthesized in the same manner.

4-n-hexyloxycinnamic acid-4'-(2-propoxypropoxy) phenyl ester, 4-n-hexyloxycinnamic acid/l-4'-(2-butoxypropoxy)
Phenyl ester, 4-n-cutyloxycinnamic acid-
4'-(2-pentyloxypropoxy) phenyl ester, 4-n-7yloxycinnamic acid-4'-(2-propoxypropoxy) phenyl ester, 4-n-dodecyloxycinnamic acid-4'-(2- Ethyloxypropoxy) phenyl ester, 4-n-tetradecyloxycinnamic acid-4-(2-hexyloxypropoxy) phenyl ester, 4-n-octylcinnamic acid-4'-(2
-octyloxypropoxy)phenyl ester, 4-
n-hexyl cinnamic acid M-4'-(2-pentyloxypropoxy) phenyl ester, 4-n-octyloxycinnamic acid-4'-(3-ethyloxy-2-methylpropyloxy cinnamic acid M-4'- (3-pentyloxy-2-
Methylpropyloxy) phenyl ester, 4-n-hexyloxycinnamic acid-4'-(4-ethyloxypentyloxy) phenyl ester, 4-n-octyloxycinnamic acid-4'-(4-propyloxy) pentyloxy) phenyl ester, 4-n-decyloxycinnamic acid-4'-(4-pentyloxypentyloxy) phenyl ester.

Synthesis of MJBU 4-n-7'siloxycinnamic s4'-(z-ethoxybropoxylponyl)phenyl ester.

(Step 1) p-Hydroxyamne, 9, aromatic acid (2-ethoxy)propyl ester.

800 sentences, 165g of P-7 cetyl oxybenzoin 50
g was added and heated at 60°C for 40 minutes. After cooling, the solvent was distilled off to obtain 5 g of CH,Coo-@-COC 64.

2-Ethoxypropanol (C2HsOC
” HCCHs )CH2 0H)l O g and N,
1.6 g of N-dimethylaniline, 20 ml of ether
CH3COO-@-C0 obtained above was dissolved in and stirred.
22.3 g of Blend C was added dropwise over 45 minutes. Thereafter, the mixture was heated and stirred for 1 hour and 30 minutes.

Water was added and the ether layer was separated and purified to obtain p-7 cetyloxybenzo W M (2-ethoxy)propyl ester. After putting methanol into it.

A mixed solution of methanol/28% aqueous ammonia = 1:1 was added and stirred for hydrolysis.

Extract with 400ml of ether, wash with water, dry (Na2SO
4) L, the solvent was distilled off to obtain 11.5 gft of crude product.

Column purification using 1 kg of silica gel (mobile phase: isopropyl ether: n-hexane = l:l), p-hydroxybenzoic m(2-ethoxy)propyl ester6.
4g is fG.

The following IR data was obtained for the product.

IR(cII+-'): P-acetyloxyamine, 9. Fragrant (2-ethoxy)propyl ester 2980.2880.1770.1720°1610
, 1505 , 1375, 1275.1200 , 1
l 60, l 120, 1100゜p-hydroxyammonium, 9. Fragrant (2-ethoxy)propyl ester 3310.2990.2900.1720°1700.
1620, 1600.1520.1450.1390.
1280.1170.1100° (Step 2) 4-n-decyloxycinnamate MF-4' (
2-(ditoxyproboxyl) phenyl ester.

4-n-decyloxycinnamic acid2. Og and thionyl chloride GvA were stirred at 30 to 40°C for 4 hours, excess thionyl chloride was distilled off under reduced pressure, and the mixture was washed with benzene to obtain a yellow oil. To this, toluene 11! IJI was added to form a solution.

1.5 g of 4-(2-ethquinpropoxycarbonyl)phenol was dissolved in 8 mg of pyridine 61-toluene and cooled. To this, the toluene solution of 4-n-decyloxycinnamate acid chloride prepared above was added dropwise at -2 to 1°C over 40 minutes, and the mixture was stirred overnight at room temperature. The mixture was poured into 8011 cups of ice water and extracted with ethyl acetate (50 mu x 3 times). Further, washing was performed successively with 6N hydrochloric acid, wood, 6% aqueous sodium bicarbonate solution, and water. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting yellow solid was subjected to silica gel column chromatography (developing solution: n-hexane/ethyl acetate = l
Purified by O/3). The obtained yellow viscous substance was recrystallized with ethanol and then methanol to give 4-n
-Decyloxycinnamate%-4'-(2-ethoxyproboxylic acid) phenyl ester 390II 1g to 7
It's 11.

The following IR data was obtained for the product.

IR (cm-'): 3450.2930.2850.1722.1639.
1617.1278.1218.1150.1120.
995. 843° The following compound is synthesized in the same manner.

4-n-hexyloxycinnamic acid-4'-(2-butyloxypropoxylponyl)phenyl ester, 4-
n-pentyloxycinnamic acid-4-(2-7'rohylboxycarponyl) phenyl ester, 4-n-octyloxycinnamic acid-4'-(2-methyloxypropoxycarponyl) phenyl ester, 4-n- Nonyloxycinnamic acid-4'-(2-hexyloxypropoxycarbonyl) phenyl ester, 4-n-decyloxycinnamic acid-4-(2-octyloxypropoxycarbonyl) phenyl ester, 4-n-hbutyl Oxycinnamic acid-4'-(2-pentyloxybroboxylic acid) phenyl ester, 4-n-cutylcinnamic acid-4
'-(2-butyloxyproboxylic acid) phenyl ester, 4-n-butyloxycinnamic acid-4'-
(4-ethyloxypentylreoxylponyl)phenyl ester, 4-n-decyloxycinnamic acid-4'-
(4-Butyloxypentyloxycarbonyl)phenyl ester, 4-n-hexyloxycinnamic acid-4-(
4-octyloxypentyloxycarbonyl) phenyl ester, 4-n-hebutylcinnamic acid-4'-(4-
butyloxypentyloxycarbonyl) phenyl ester.

3-(p-n-decyloxyphenyl)propion M4
'Synthesis of (2-ethoxypropoxy)phenyl.

3-(pn-decyloxyphenyl)propion IV
2, 4 g, 1i thionyl trichloride 7I19. In addition,
It was refluxed for 4 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain acid 18 compound.

Next, 4-(2-ethoxypropoxy)phenol 1.5
A 10+ai solution of the above acid chloride in toluene was added dropwise at 5° C. or below into an 8M solution of pyridine (g) at t:0. After the dropwise addition, the mixture was stirred at room temperature for 19 hours and poured into ice water. Separate the organic layer;
The aqueous layer was extracted with ethyl acetate, combined with the organic layer, and 6Nj! !
Wash with acid, water, 2N Na0H aqueous solution, and water in this order, and add anhydrous M
It was dried with g5O. The solvent was distilled off, and silica gel column chromatography (n-hexane:ethyl acetate=lO:l
) to obtain 2.3 g of crystals. This was treated with activated carbon in an ethanol solvent, and 4'-(2-ethoxypropoxy)phenyl 3-(p-n-decyloxyphenyl)propionic acid1. Obtained Og.

IR (c-1): 2970-2860.1750.1510.1250.
1210.1150. 840° Phase transition temperature: The following compounds are synthesized in the same manner.

3-(p-n-hexyloxyphenyl)propionic acid-4'-(2-propyloxypropoxy)phenyl,
3-(pn-octylleoxyphenyl)propion M-4”-(2-methyloxypropoxy)phenyl,
3-(p-n-/nyloxyphenyl)propionic acid-
4'-(2-octyloxypropoxy)phenyl, 3
-(p-n-decyloxyphenyl)propionic acid-4
'-(2-pentyloxypropoxy)phenyl, 3-
(p-n-dodecyloxyphenyl)flopion M-4
'-(2-hexyloxypropoxy)phenyl, 3-
(p-n-octyloxyphenyl)propionic acid-4
'-(4-ethyloxypentyloxy)phenyl, 3
-(p-n-decyloxyphenyl)propionic acid-4
-(4-butyloxypentyloxy)phenyl, 3-
(p-n-octyloxyphenyl)propionic acid-4
'-(3-pentyloxy-2-methylpropyloxy)phenyl, 3-(p-n-decyloxyphenyl)propion M-4'-(2-ethoxypropyloxypropyl)phenyl, 3-(p- n-octyloxyphenyl)propionic acid-4'-(2-butyloxypropyloxytriponyl)phenyl, 3-(p-n-decyloxyphenyl)propion A6-4'-(4-propyloxypentyloquinecarponyl) ) phenyl, 3-(
p-n-octyloxyphenyl) fropion Me-4
'-(4-pentyloxypentyloxycarbonyl)
Phenyl, 4'-(2-butyloxypropoxy)phenyl 3-(p-n-octylphenyl)furopionate.

History JJL4 Synthesis of 3-4'-(2-ethoxypropoxy)phenyl 3-(p-n-decyloxyphenyl)thiopropionic acid (Step 1) 2-ethoxypropyloxybenzene dry pyridine 240+aJ1 and 2-ditoxypropionate tool 45
Add 73 g to the flask, cool with water while stirring, and add to the tuna.
After adding P-) luenesulfonic acid chloride in small portions and reacting for 2 hours.

The temperature was returned to room temperature and the reaction was continued for an additional 4 hours. 6% ice-cold
The reactants were added to a HC aq and stirred, then extracted with benzene and dried over anhydrous Na2sO*. Benzene was distilled off to obtain 96 g of oily (2'-ethoxypropyl) p-)luenesulfonate.

Mix 38.6 g of phenol and 23 g of 85% KOH with methanol.
After adding 3 m of Ceftain and stirring with 446 m of ethanol. Add to this the (2'-ethoxypropyl) obtained above.
- Add 91 g of p-toluenesulfonate, and add 60 to 70 g.
After stirring at ℃ for 2 hours, the mixture was reacted under heating under reflux for 7 hours, and then ethanol was distilled off. 1500 mA of water was added to the residue, and after extraction with ether, the ether was distilled off from the extract, and the residue was subjected to silica gel column chromatography (using a hexane:chloroform=5=1 mixture as a solution)
Purified by 2-ethoxypropyloxybenzene 4
9.3g was obtained. Its IR (infrared absorption) data is as follows.

IR (cm-'): 3070-3040.2970-2980°1600-
1582.1495.1243° (Step 2) 4- (2
'-Ethoxypropyloxy)benzenethiol 49 g of 2-ethoxypropyloxybenzene obtained in step 1 above was dissolved in 130 mJ1 of chloroform and cooled to -10°C in a water bath. Among them, Cl5O, H63
, 5g was gradually added dropwise. Thereafter, the water bath was removed, and the mixture was stirred for 5 hours to react, then poured onto ice and neutralized with an aqueous NaOH solution. Further, the solvent was removed and 4(2'-ethoxypropyloxy)benzenesulfone a l l 6 g
I got it.

562.4 g of PCl was gradually added to the mixture of 116 g of 4(2'-ethoxypropyloxy)benzenesulfonic acid obtained above and 500 g of dry benzene at room temperature. After that, after heating to 60°C and reacting for 6 hours,
The organic layer was poured onto ice, washed with water, dried, and the solvent was removed to obtain an oily liquid. This was subjected to silica gel column chromatography (n-hexane:isopropyl ether = 3:l).
) to obtain 15 g of 4(2'-ethoxypropyloxy)benzenesulfonic acid chloride.

Next, a mixture of 110 g of ice and 36 g of concentrated sulfuric acid was added to the water bath for 15 minutes.
The mixture was cooled to 0.degree. C., and 15 g of the above 4(2'-ethoxypropyloxy)benzenesulfonic acid chloride was gradually added dropwise thereto. Thereafter, 28.6 g of Zn was added. After stirring for 2 hours.

The water bath was removed 5 and the temperature was gradually raised to 55°C. After further stirring at the same temperature for 2 hours, the mixture was cooled and the reaction solution was extracted with isopropyl ether. After washing the extract with water and drying, the solvent was removed to obtain a colorless liquid. This was purified using a silica gel column (n-hexane:ethyl acetate=5:1) to obtain 8 g of 4(2'-ethoxypropyloxy)benzenethiol.

IR (cm-'): 2970-2880, 2550.1600°1500.
1285.1245.1105° (Step 3) 3-(p-n-7'' syloxyphenyl)thiopropionic acid S-4'-(2-ethoxypropoxy)phenyl ester.

Ii! 5tan of thionyl chloride was added and the mixture was refluxed for 4 hours. Excess 1,000 onyl chloride was distilled off under reduced pressure to obtain acid chloride. 1.39 g of 4-(2-ethoxypropoxy)phenylthiol was dissolved in 8 ml of pyridine, and in this solution, the above-mentioned Acid chloride toluene 10 II
The +u solution was added dropwise at a temperature below 5° C. After 0 dropwise addition, the mixture was stirred at room temperature for 200 hours and placed in ice water. The aqueous layer was extracted with ethyl acetate, combined with the organic layer, and extracted with 5% 11X acid aqueous solution twice, water once, and 5% NaOH aqueous solution once.
It was washed twice with wood and dried with Glauber's salt. Remove the solvent,
Silica gel column chromatography (n-hexane:
Purification was performed using ethyl acetate (lO:3) to obtain 2.2 g of crystals. This was treated with activated carbon in an ethanol solvent, and 3-(p
-n-decyloxyphenyl)thiopropionic acid S-4
'-(2-ethoxypropoxy)phenyl 1.15g! It was.

IR (cm-'): 2970~2860.1720.1530°1280~
1260.1050.840° Phase transition temperature (°C) The following compounds are synthesized in the same manner.

3-(p-n-octyloxyphenyl)thiopropionic acid-3-4'-(2-butyloxypropoxy)phenyl, 3-(p-n-hebutyloxyphenyl)thiopropionic acid-5-4'- (2-pentyloxypropoxy)phenyl, 3-(p-n-decyloxyphenyl)
5-4'-(2-octyloxypropoxy)phenyl thiopropionate, 3-(p-n-octyloxyphenyl)thiopropionate-5-4'-(2-octyloxypropoxy)pheny JL/, 3 -(P-n-decyloxyphenyl)thiopropionic acid-5-4'-(2
-ethyloxypropoxy)phenyl, 3-(p-n-
octyloxyphenyl)thiopropionic acid-5-4'
-(4-ethyloxypentyloxy)phenyl, 3-
(p-n-decyloxyphenyl)thiopropion 11
-3-4"-(pentyloxypentyloxy)phenyl, 4-n-decyloxythiocinnamic acid-3-4'-(
2-ethyloxypropyloxy)phenyl, 4-n-
5-4'-(4-Butyloxypentyl)phenyl octyloxythiocinnamate.

Rikunn GR-63 (Biphenyl liquid crystal mixture manufactured by Chisso)
A TN cell using a liquid crystal mixture prepared by adding 1 part by weight of 4'-(2-ethoxypropoxy)phenyl 3-(p-n-decyloxyphenyl)propionate to 99 parts by weight of this optically active 3- The r51 K(
It was done.

Polyimide film (polyamic acid resin consisting of a combination of pyromellitic anhydride and 4,4'-diaminodiphenyl ether) with a film thickness of 1000 on each of the opposing matrix electrodes formed of crossed ITO strips. A 5% by weight N-methylpyrrolidone solution was coated on the polyimide film (formed by a ring-closing reaction under heating at a temperature of 250°C), and the surfaces of this polyimide film were rubbed so that they were parallel to each other, so that the cell thickness was 17L. Created a cell.

Next, the following composition A was injected into the above-mentioned cell by a vacuum injection method under the same phase, and the cell was sealed. After that, slow cooling (
A liquid crystal cell of ``Smc'' was prepared using 1'c/hour).

Liquid crystal composition ΔU 5% by weight 15% by weight 5% by weight A crossed Nicol polarizer and an analyzer were placed on both sides of this liquid crystal cell, and the waveforms shown in FIGS. 4 and 5 were measured between the facing matrix electrodes. A signal was applied. At this time, the scanning signal is as shown in Figure 4 (
The alternating waveforms of +8 volts and 18 volts shown in &) were used, and the written information was set to +4 volts and 14 volts, respectively.

In addition, the interval between l frame t and lll1 was set to 30 masec.

As a result, this liquid crystal element can be used for the above-mentioned memory-driven hour/minute
1. Even when the II drive was performed, the written state was not reversed and a normal moving image display was obtained.

The following comparative liquid crystal B was prepared by omitting the optically active liquid crystal compound represented by the above-mentioned general formula (I) in the liquid crystal composition used to create the liquid crystal element of Example 6: A liquid crystal was manufactured using a liquid crystal for comparison. These liquid crystal elements were driven in the same manner as described above, but normal movement 1ijIi was not displayed due to an inversion phenomenon.

Stop ■Placement”

[Brief explanation of drawings]

1 and 2 are perspective views schematically showing a time-division driving liquid crystal element used in the present invention, FIG. 3 is a plan view of a matrix electrode structure used in the present invention, and FIGS. (d
) is an explanatory diagram representing the electric signal applied to the matrix electrodes, FIGS. 5(a) to (d) are explanatory diagrams representing the waveform of the voltage applied between the matrix electrodes, and FIG. FIG. 3 is an explanatory diagram of a time chart showing an electric signal applied to a liquid crystal element. 11a, 1lb==substrate. 12...Liquid crystal molecule layer, 13...Liquid crystal molecule. 14...Dipole moment (P). 23a...First stable state, 23b...Second stable state, 24a...Upward dipole moment. 24b...Downward dipole moment, 31...Cell, 32...(s,, S2.33....)...Scanning electrode group, 33...(Il, I2.r3,... ...)...Signal electrode group. Certain f Figure 2 Figure 33a Electrode Group II 12 13 14 15 ---- Drainage 3 Figure 4 Figure (Burning) Figure 5

Claims (1)

[Claims] 1. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* indicates an asymmetric carbon atom, R^1 indicates an alkyl group or alkoxy group having 4 to 18 carbon atoms, X is -CH_
2-CH_2- or -CH=CH-, Z is -
Indicates O- or -S-. n indicates 0 or 1, l
represents 0 or 1, and m represents 1 to 8. ) An optically active liquid crystal compound represented by 2. General formula (I) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* represents an asymmetric carbon atom, and R^1 represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms. X is -CH_
2-CH_2- or -CH=CH-, Z is -
Indicates O- or -S-. n indicates 0 or 1, l
represents 0 or 1, and m represents 1 to 8. ) A liquid crystal composition comprising at least one optically active liquid crystal compound represented by the following. 3. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (However, R represents an alkyl group having 1 to 18 carbon atoms, and C
^* represents an asymmetric carbon atom, and R^1 represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms. X is -CH_
2-CH_2- or -CH=CH-, Z is -
Indicates O- or -S-. n indicates 0 or 1, l
represents 0 or 1, and m represents 1 to 8. ) A liquid crystal element using a liquid crystal composition containing at least one type of optically active liquid crystal compound represented by: