JPH0621115B2 - Hydroxyvaleric acid derivative and liquid crystal composition containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an optically active hydroxyvaleric acid derivative and a liquid crystal composition containing the same, and more specifically to a liquid crystalline compound which is an optically active hydroxyvaleric acid derivative. The present invention relates to a liquid crystal composition containing it and a liquid crystal device using the liquid crystal composition.

Background Art As a conventional liquid crystal element, for example, M-shut (MS
chadt) and W. Helfrich
Written, "Applied, Physics, Letters" Vol. 18 4
Issue ("Applied Physics Letters", Vol.18, No.4)
(1971.2.15), “Voltage-dependent optical behavior of twisted nematic liquid crystals” on pages 127-128 (“Voltage-Dependent Optimal”).
cal Activity of a Twisted Nematic Liquid Crysta
TN (Twisted nematic)
A liquid crystal is known. However, this TN liquid crystal has a problem that crosstalk occurs during time-divisional driving using a matrix electrode structure having a high pixel density, and thus the number of pixels is limited. Further, since the electric field response is slow and the viewing angle characteristic is poor, the use as a display is limited.

Furthermore, a display element of a type in which a switching element using a thin film transistor is connected to each pixel and switching is performed for each pixel is known, but a process of forming a thin film transistor on a substrate is extremely complicated, and a large area display element is used. There are problems that are difficult to create.

The use of bistability-type liquid crystal elements is one of the ways to improve the drawbacks of the conventional type liquid crystal elements.
ark) and Lagerwall (JP-A-56-107216, US Pat. No. 4,367,924, etc.). As a liquid crystal having bistability, generally,
Chiral smectic C phase (SmC ^* ) or H phase (S
Ferroelectric liquid crystals with mH ^* ) are used.

Since this ferroelectric liquid crystal has spontaneous polarization, it has a very fast response speed, and can express a bistable state with a memory property, and also has excellent viewing angle characteristics. Suitable as

Since the liquid crystalline compound used for the ferroelectric liquid crystal has an asymmetric carbon, it can be used for the following optical elements as well as the ferroelectric liquid crystal using its chiral smectic phase. Can be used.

1) Utilizing the cholesteric / nematic phase transition effect in the liquid crystal state (JJWysoki, A. Adams and WH
aas; Phys.Rev.Lett., 20,1024 (1968)), 2) Utilizing the white Taylor type guest-host effect in the liquid crystal state (DLWhite and GNTaylor;
J.Appl. Phys., 45 , 4718 (1974)), 3) By fixing the one that has a cholesteric phase in the liquid crystal state in the matrix, and utilizing its selective scattering characteristics, it can be used as a notch filter or bandpass filter. Things to do (FJKahn, Appl.Phys.Lett., 18,231
(1971)), which is used as a circularly polarized beam splitter utilizing circular polarization characteristics (SDJacobs, SPIE, 37,98 (198
1)): etc.

A detailed description of each method is omitted, but all are important as a display element or a modulation element.

Conventionally, a functional material required for an optical element having optical activity is an optically active intermediate for synthesizing 2-methylbutanol, a secondary octyl alcohol,
Secondary butyl alcohol, p- (2-methylbutyl) chloride
Benzoic acid, secondary phenethyl alcohol, amino acid derivatives, camphor derivatives, cholesterol derivatives and the like are known.

However, these have the following drawbacks. The structure of the optically active chain hydrocarbon derivative is difficult to change, and, except for some, it is very expensive. Amino acid derivatives are relatively inexpensive and their structures can be easily modified, but the hydrogen groups of amines are chemically strongly active, and hydrogen bonding and chemical reactions are likely to occur, which tends to limit the properties of functional materials. . The camphor derivative and the cholesterol derivative are difficult to change their structures, and moreover, they tend to adversely affect the properties of the functional material due to steric hindrance.

The above-mentioned drawbacks have been a major limitation in developing various materials.

Object of the Invention In view of the above circumstances, a main object of the present invention is to provide an optically active compound useful for controlling a liquid crystal state, and a liquid crystal composition containing the same.

More specifically, the present invention can bond a functional material intermediate having an appropriate intermolecular force and shape for forming a liquid crystal, an LB film, a bilayer film, etc., without impairing the optical activity. The present invention aims to provide a compound which is crystalline and can be designed freely, and which is itself crystalline.

Another object of the present invention is to provide a compound which causes large spontaneous polarization when used as a ferroelectric liquid crystal due to the presence of an oxygen atom adjacent to an asymmetric carbon atom.

Further, according to the present invention, it is easy to change the length of the alkyl group, which allows the H.Arnold, Z.Phys.Chem., 226 , 146 (1
964), a liquid-phase compound capable of controlling the type and temperature range of a liquid crystal phase developed in a liquid crystal state, and a liquid crystal composition containing the liquid phase compound as at least one compounding component. And

Another object of the present invention is to provide a compound capable of easily controlling a hydrophobic group and stably forming a film when a monomolecular cumulative film is produced by the LB (Langmuir-Blodgett) film method. .

SUMMARY OF THE INVENTION That is, the present invention provides a compound represented by the general formula (I) [In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms, and C ^* represents an asymmetric carbon atom. l is 0 or 1, and when l = 1, m and n are 0 or 1. A is (However, R ¹ represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms, Respectively Where p, q and r are 0 or 1 and p + q + r ≧ 1
The optically active hydroxyvaleric acid derivative represented by the formula (1) and a liquid crystal composition containing the derivative as at least one compounding component are provided.

Especially A The above-mentioned optically active hydroxyvaleric acid derivative itself exhibits liquid crystallinity, and a liquid crystal composition having good characteristics can be obtained by containing at least one kind of compounding ingredient. The present invention also provides a liquid crystal device using such a liquid crystal composition.

DETAILED DESCRIPTION OF THE INVENTION In the general formula (I) showing the optically active substance, R is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms. When it is 19 or more, the viscosity and molar volume of the final functional material increase, which is not preferable. The preferred number of carbon atoms of R is 4 to 1
It is 6. Specific examples of R include linear alkyl group, branched alkyl group, cycloalkyl group, linear alkenyl group, branched alkenyl group, cycloalkenyl group, linear alkadienyl group, branched alkadienyl group, cyclo Examples include an alkadienyl group, a linear alkatrienyl group, a branched alkatrienyl group, a linear alkynyl group, a branched alkynyl group, and an aralkyl group. An alkyl group is particularly preferable for providing a liquid crystal compound. Also, C ^*
Represents an asymmetric carbon atom. In the above general formula (I) structure, a liquid crystal compound comprising the optically active hydroxyvaleric acid derivative of the present invention can be obtained by changing various reagents to be reacted with the optically active intermediate in which A is a hydroxyl group. .

That is, A (However, R ¹ represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms, Respectively Where p, q and r are 0 or 1 and p + q + r ≧ 1
The relationship of (1) is satisfied, and the optically active valeric acid derivative of the present invention is obtained. In this case, the particularly preferable number of carbon atoms of R ¹ is 6 to 16.

Next, an example of a method for synthesizing the optically active hydroxyvaleric acid derivative represented by the general formula (I) of the present invention will be shown.

RI in the above reaction formula can be selected over a wide range of carbon numbers, and specifically, iodobutane,
Iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, iodoundecane, iododecane, iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, iodoheptadecane, iodooctadecane, iodononadecane, iodoeicosane, etc. Chained saturated hydrocarbon iodide; branched saturated hydrocarbon iodide such as 2-iodobutane, 1-iodo-2-methylpropane, 1-iodo-3-methylbutane; iodobenzyl, iodophenacyl, 3-iodo-1-cyclohexene Iodocyclopentane, iodocyclohexane, 1-iodo-3-methylcyclohexane, iodocycloheptane, iodocyclooctane, etc. cyclic unsaturated hydrocarbon iodide There is.

By freely selecting from the above iodides, R
It is possible to obtain optically active hydroxyvaleric acid derivatives (b) different from each other.

The hydroxyvaleric acid derivative of the present invention shown below by the synthetic route shown below by the obtained hydroxyvaleric acid derivative (b) Is obtained.

(In the above, R, R ¹ and 1, m, n, p, q, r
Is as defined above. An example of the liquid crystalline hydroxyvaleric acid derivative thus obtained is shown in Table 1 below.

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

Cryst .: crystalline phase, SmA: smectic A phase, SmC ^* : chiral smectic C phase, N: nematic phase, Ch .: corsteric phase, Iso: isotropic phase, Sm3: SmA, smectic phase other than SmC ^* (not yet Identification).

Further, the following compounds can be obtained based on the compounds shown in Table 1 and the above-mentioned synthetic methods.

The liquid crystal composition of the present invention contains at least one kind of optically active liquid-phase hydroxyvaleric acid derivative represented by the above general formula (I) as a blending component.

Among the above-mentioned compositions, those containing a ferroelectric liquid crystal as represented by the following formulas (1) to (13) as a blending component can increase spontaneous polarization and further reduce the viscosity. This is preferable because it can improve the response speed. In such a case, the hydroxyvaleric acid derivative of the present invention represented by the general formula (I) is preferably used in a ratio of 0.1 to 99% by weight, particularly preferably 1 to 9
Used at 0% by weight.

(1) 4-octyloxybenzoic acid 4 '-(2-methylbutyloxy) phenyl ester (2) 4-nonyloxybenzoic acid 4 '-(2-methylbutyloxy) phenyl ester (3) 4-decyloxybenzoic acid 4 '-(2-methylbutyloxy) phenyl ester (4) 4-Undecyloxybenzoic acid 4 '-(2-methylbutyloxy) phenyl ester (5) 4-dodecyloxybenzoic acid 4 '-(2-methylbutyloxy) phenyl ester (6) P-decyloxybenzylidene-P'-amino-2--methylbutyl cinnamate (DOBAMBC) (7) 4,4'-azoxycinnamic acid-bis (2-
Methyl butyl) ester (8) 4-o- (2-methyl) -butylresorcylidene-4 '
-Octylaniline (MBRA 8) (9) 4- (2'-methylbutyl) phenyl-4'octyloxybiphenyl-4-carboxylate (10) 4-hexyloxyphenyl-4- (2 "-methylbutyl) biphenyl-4'-carboxylate (11) 4-octyloxyphenyl-4- (2 "-methylbutyl) biphenyl-4'-carboxylate (12) 4-heptylphenyl-4- (4 "-methylhexyl)
Biphenyl-4'-carboxylate (13) 4- (2 "-methylbutyl) phenyl-4- (4" -methylhexyl) biphenyl-4'-carboxylate Further, by compounding with a smectic liquid crystal which is not chiral itself as shown in the following formulas 1) to 5), a composition usable as a ferroelectric liquid crystal can be obtained.

In such a case, the optically active liquid crystalline compound which is the hydroxyvaleric acid derivative of the present invention represented by the general formula (I) can be used in a ratio of 0.1 to 99% by weight.

1) (4-nonyloxyphenyl) -4'-octyloxybiphenyl-4-carboxylate 2) 4,4'-decyloxyazoxybenzene 3) 2- (4'-hexyloxyphenyl) -5- (4-hexyloxyphenyl) pyrimidine 4) 2- (4'-octyloxyphenyl) -5-nonylpyrimidine 5) 4'-Ventyloxyphenyl-4-octyloxybenzoate Here, the symbols indicate the following phases, respectively.

Cryst .: Crystal phase, SmA: Smectic A
Phase, SmB: smectic B phase, SmC: smectic C phase, N: nematic phase, Iso .: isotropic phase.

Further, the nematic liquid crystal containing the hydroxyvaleric acid derivative of the present invention as at least one compounding component is preferable because it can prevent the generation of a reverse domain when used in a twisted nematic (TN) type cell.

When an element is formed using these liquid crystal materials, the element is provided with a copper block or the like in which a heater is embedded, if necessary, in order to keep the liquid crystal material in a temperature state such that it is in the SmC ^* phase or the SmH ^* phase. Can be supported.

FIG. 1 is a schematic drawing of an example of a cell for explaining the operation of the ferroelectric liquid crystal. And 11a, 11b, respectively _In 3 _O 3, SnO ₂ or ITO (Indium-
Tin 0xide) is a substrate (glass plate) covered with a transparent electrode composed of a thin film such as SmC ^c phase or SmH ^{* in} which the liquid crystal molecular layer 12 is oriented perpendicular to the glass surface ^.
The liquid crystal of the phase is enclosed. A thick line 13 represents a liquid crystal molecule, and this liquid crystal molecule 13 has a dipole moment (P⊥) 14 in a direction orthogonal to the molecule. When a voltage above a certain threshold is applied between the electrodes on the substrates 21 and 11b, the helical structure of the liquid crystal molecules 13 is unraveled,
The liquid crystal molecules 13 can change the orientation direction so that all the dipole moments (P⊥) 14 are oriented in the electric field direction.
The liquid crystal molecules 13 have an elongated shape and exhibit refractive index anisotropy in the major axis direction and the minor axis direction thereof. Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, the voltage application polarity is It can be easily understood that the liquid crystal optical modulation element changes its optical characteristics depending on the situation.

The liquid crystal cell preferably used in the optical modulator of the present invention can be made sufficiently thin (for example, 10 μm or less). As the liquid crystal phase becomes thinner like this,
As shown in FIG. 2, even when no electric field is applied, the helical structure of the liquid crystal molecules is unraveled, and its dipole moment Pa
Alternatively, Pb is either in the upward (24a) or downward (24b) state. When an electric field Ea or Eb having a polarity equal to or higher than a certain threshold value is applied to such a cell by the voltage applying means 21a and 21b, the dipole moment corresponds to the electric field vector of the electric field Ea or Eb. Then, the liquid crystal molecules are turned upward 24a or downward 24b, and accordingly, the liquid crystal molecules are oriented to either the first stable state 23a or the second stable state 23b.

As described above, there are two advantages of using such ferroelectricity as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the alignment of the liquid crystal molecules has bistability. The second point will be further described with reference to FIG. 2, for example.
When the voltage is applied, the liquid crystal molecules are aligned in the first stable state 23a, but this state is stable even when the electric field is cut off. When a reverse electric field Eb is applied, the liquid crystal molecules are oriented in the second stable state 23b to change the orientation of the molecules, but they remain in this state even when the electric field is cut off. Also, the applied electric field E
As long as a or Eb does not exceed a certain threshold value, the previous orientation state is still maintained. In order to effectively realize such a high response speed and bistability, it is preferable that the cell is as thin as possible, generally 0.5
μ to 20 μ, particularly 1 μ to 5 μ are suitable.

Next, a specific example of the driving method of the ferroelectric liquid crystal will be described with reference to FIGS.

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. Reference numeral 32 is a scan electrode group, and 33 is a signal electrode group. First, the case where the scan electrode S ₁ is selected will be described. 4 (a) and 4 (b) show scanning signals, which are electric signals applied to the selected scanning electrode S ₁ and the other scanning electrodes (unselected scanning electrodes) S, respectively.
₂ shows electric signals applied to S ₃ , S _4, ... 4 (c) and 4 (d) show information signals which are electric signals applied to the selected signal electrodes I ₁ , I ₃ , I ₅ and the unselected signal electrodes I ₂ , I ₄ , respectively. Shows.

4 and 5, the horizontal axis represents time and the vertical axis represents voltage. For example, when displaying a moving image, the scan electrode group 32 is sequentially and periodically selected. Now, a threshold voltage for giving a first stable state of a liquid crystal cell having bistability for a predetermined voltage application time t ₁ or t ₂ is −Vtn _1, and a threshold value for giving a stable state of 2 is set. When the voltage is + Vth ₂ , the electrode signal applied to the selected scan electrode 32 (S ₁ ) is 2V at the phase (time) t _{1 and the} phase (time) t at the phase (time) t ₁ as shown in FIG. _{At 2} , the alternating voltage is -2V. When electric signals having a plurality of phase intervals different from each other in voltage are applied to the selected scan electrodes in this way, the liquid crystal is switched between the first and second stable states of the liquid crystal corresponding to the optical “dark” or “bright” state. An important effect is that the state change of can be promptly caused.

On the other hand, other scanning electrode _S 2 _{to S} 5 · · · is a ground state, as shown in FIG. 4 (b), an electric signal 0
Is. In addition, the electric signal applied to the selected signal electrodes I ₁ , I ₃ , and I ₅ is V as shown in FIG. 4 (c).
And the electrical signal applied to the unselected signal electrodes I ₂ and I ₄ is −V as shown in FIG. 4 (d). In the above, each voltage value is set to a desired value that satisfies the following relationship.

V <Vth ₂ <3V −3V <−Vth ₁ <−V Among the respective pixels when such an electric signal is given, for example, the voltage waveforms applied to the pixels A and B in FIG. 5 is shown in FIGS. That is, as is apparent from FIGS. 5A and 5B, in the pixel A on the selected scanning line, the voltage 3V exceeding the threshold value Vth ₂ is applied at the phase t ₂ . Further, in the pixel B existing on the same scanning line, the voltage −3V exceeding the threshold −Vth ₁ is applied at the phase t ₁ . Therefore, on the selected scan electrode line, depending on whether or not the signal electrode is selected, the liquid crystal molecules are aligned in the first stable state when selected, and the liquid crystal molecules are aligned in the first stable state when not selected. Align the orientation to the stable state of 2.

On the other hand, as shown in FIGS. 5 (c) and 5 (d), the voltage applied to all pixels is V
Or, it is -V, and neither exceeds the threshold voltage. Therefore, the liquid crystal molecules in each pixel other than on the selected scanning line maintain the orientation corresponding to the signal state at the time of the previous scanning without changing the orientation state. That is, when the scan electrode is selected, the signal for one line is written, and the signal state can be held until the end of one frame and the next selection. Therefore, even if the number of scan electrodes is increased, the substantial duty ratio remains unchanged, and the contrast is not deteriorated at all.

Next, let us consider the problems that may actually occur when the display device is driven. In Figure 3,
The scan electrodes S _{1 to} S ₅ ... And the signal electrodes I _{1 to} I ₅ ...
Among the pixels formed at the intersections, the shaded pixels correspond to the “bright” state, and the pixels shown on a white background correspond to the “dark” state. Now, paying attention to the display on the signal electrode I _{1 in} FIG. 3, the pixel (A) corresponding to the scan electrode S ₁ is in the “bright” state, and the other pixels (B) are all in the “dark” state. Is. As an example of the driving method in this case, FIG. 6 shows the scanning signal, the information signal given to the signal electrode I ₁ and the voltage applied to the pixel A in time series.

For example, when driven as shown in FIG. 6, the scanning signal S
_{When 1} is scanned, the voltage 3V exceeding the threshold value Vth ₂ is applied to the pixel A at the time t ₂ , so that the pixel A is stable in one direction, that is, the “bright” state regardless of the previous history. Switch to. Thereafter, S ₂ to S ₅ · · · although while being scanned continuously applied voltage of -V as shown in FIG. 6, the pixels A This will not exceed the threshold value -Vth ₁
Should be able to maintain the "bright" state, but in actuality, in the case of displaying information such that one signal (corresponding to "dark" in this case) is continuously given on one signal electrode. Has an inversion phenomenon when the number of scanning lines is extremely large and high-speed driving is required. By using the above-mentioned specific liquid crystal compound or a liquid crystal composition containing the same, such inversion phenomenon is completely eliminated. To be prevented.

Further, in the present invention, in order to prevent the above-mentioned inversion phenomenon, it is preferable to provide an insulating film formed of an insulating material on at least one of the directional electrodes forming the liquid crystal cell.

The insulating material used at this time is not particularly limited, but silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, hydrogen. Containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, inorganic insulating materials such as titanium oxide and magnesium fluoride, or polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyvaraxylene, polyester, An organic insulating material such as polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin or photoresist resin is used as the insulating film. The thickness of these insulating films is 5000 Å or less, preferably 10
0Å to 1000Å, particularly 500Å to 3000Å are suitable.

EFFECTS OF THE INVENTION The optically active hydroxyvaleric acid derivative of the present invention can control the type and temperature range of the liquid crystal phase that appears in the liquid crystal state by selecting the length of the alkyl group. Further, a liquid crystal composition containing at least one kind of the optically active liquid crystalline hydroxyvaleric acid derivative of the present invention as a compounding component is used as a chiral nematic liquid crystal or a chiral smectic liquid crystal to increase spontaneous polarization and increase the viscosity. Through adjustments, etc., it is possible to improve response speed and prevent reverse domain from occurring.

Hereinafter, the optically active substance and the liquid crystalline compound of the present invention will be described more specifically with reference to Reference Examples (Production Examples of Intermediates) and Examples.

Reference Example 1 (S) -4-octyloxypentanol was produced by the following steps.

L (+)-ethyl lactate 98g, octyl iodide 380g
And 245 g of silver oxide were added, and the mixture was stirred at 60 ° C. for 16 hours. After passing the insoluble matter, it was distilled under reduced pressure to obtain 110-130 ° C /
77 g of ethyl 2-octyloxypropionate was obtained as a fraction of 3 mmHg.

Next, 250 mL of diethyl ether was added with LiA1H ₄ 7.5.
After adding g and stirring for a while, a solution of 56 g of the above ester compound in 50 ml of diethyl ether was added dropwise at 5 ° C. or lower over 2 hours, and after the addition, the mixture was stirred at room temperature for 2 hours and left for 15 hours. After completion of the reaction, 30 ml of 5% hydrochloric acid was added, and the mixture was acidified with 6N hydrochloric acid to make it acidic (pH ~ 1) and extracted with ether. After washing with water, it was dried and the solvent was distilled off. Vacuum distillation, 107 ℃
As a fraction of / 3 mmHg, 39.5 g of 2-octyloxypropanol was obtained.

Next, 230 ml of pyridine was added to 70 g of the above alcohol compound, and 85 g of tosyl chloride was stirred at 10 ° C or lower for 3 times.
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, extraction with benzene, washing with 5% hydrochloric acid and water in this order, and drying.
Benzene was distilled off, and (2-octyloxypropyl) p
-127 g of toluene sulphonate are obtained.

95% sodium ethoxide-2 in 220 ml ethanol
6.7 g was added, and 98% diethyl malonate 73.
1 g was added dropwise at 36 to 38 ° over 50 minutes. 3 more
After stirring for 0 minutes, 127 g of the tosylate body was added to 36 to 38
The solution was added dropwise at 0 ° C over 1 hour. After further stirring for 15 minutes, the temperature was raised and the mixture was refluxed for 18 hours. After the reaction, ice water was added, benzene was extracted, washed with water and dried. The solvent was distilled off and 149 g of 4-
Obtained ethyl octyloxy-2-ethoxycarbonyl valerate.

Next, 88.5 g of 85% KOH was dissolved in 90 ml of water, and 149 g of the ester compound was added dropwise at 20 to 25 ° C. over 50 minutes, stirred for 30 minutes and then refluxed for 2 hours. After cooling, 15 ℃
Keeping the temperature below, 153 g of concentrated sulfuric acid was dissolved in 196 ml of water, and this was added dropwise over 1 hour. After stirring for 30 minutes, the mixture was refluxed for 3 hours. After cooling to room temperature, it was extracted with benzene. The benzene layer was washed with a 5% NaOH aqueous solution and added to the aqueous layer. The aqueous layer was acidified (pH 1) with 6N hydrochloric acid, extracted with benzene, washed with water, and dried over anhydrous MgSO ₄ . The solvent was distilled off to obtain 54 g of 4-octyloxyvaleric acid.

To 210 ml of dry ether, 10 g of LiA1H ₄ was added and, with stirring, a solution of 54 g of the above carboxylic acid in 70 ml of ether was added.
The solution was added dropwise over 70 minutes while maintaining the temperature at 2 to 6 ° C. After dropping
It heated up to 23 degreeC and stirred for 3 hours. After leaving for 12 hours, 5
% Hydrochloric acid was added while keeping it at 15 ° C. or lower, acidified with hydrochloric acid, extracted with ether, washed with water, 5% aqueous solution of NaOH and water in this order and dried over anhydrous MgSO ₄ . The solvent was distilled off, and the residue was distilled under reduced pressure to obtain (S) -4- as a fraction at 150 ° C / 5 mmHg.
10 g of octyloxypentanol was obtained.

The following IR (infrared absorption) data was obtained for the product.

IR (cm < ^-1 >): 3360, 2970-2860, 1460, 1370, 1340, 1080.

Reference Examples 2 to 3 The following compounds were synthesized by the same synthetic method as in Reference Example 1. The product is shown along with its IR data.

-(S) -4-propoxy pentanol IR (cm < ^-1 >): 3370,2970-2870,1460,1370,1340,1080.

-(S) -4-Pentyloxypentanol IR (cm < ^-1 >): 3360, 2970-2870, 1460, 1370, 1340, 1080.

Reference Example 4 Production of (R) -4-propoxypentanol 160 g of D-methyl lactate (Methy1-D-Lactate) and 1-
524 g of iodopropane was mixed into a four-necked flask, and 471 g of newly synthesized Ag ₂ O was slowly added. Next, after stirring at a liquid temperature of 60 to 65 ° C. for 1 hour, then,
The excess was thoroughly washed with ether, the liquid ether was distilled off, and the residue was distilled under reduced pressure to obtain 161 g of methyl-2-propoxypropioneo.

Next, 35.3 g of LiA1H ₄ was added to 750 ml of ether, stirred for 3 hours and kept at 10 ° C. or lower, and a solution of 161 g of methyl-2-propoxypropionate obtained above and 150 ml of ether was added in 3.5 hours. Dropped. After the completion of dropping, the liquid temperature was stirred at 17 to 20 ° C. for 2.5 hours, and the mixture was left standing at room temperature for 12 hours. Then, it was made acidic (pH 1) with a 5% aqueous hydrochloric acid solution and extracted with ether. The ether layer was washed with water, a 5% NaHCO ₃ aqueous solution and water in this order, and dried over anhydrous magnesium sulfate. And vacuum distill,
When the fraction of 5-103 ℃ / 150mmHg is collected, 72g of 2
-Propoxy propanol was obtained.

Next, 70 g of 2-propoxypropanol was mixed with 11 g of pyridine.
4 ml and 228 ml of benzene were added, and while maintaining the solution at 10 ° C or lower with stirring, 11.5 g of methanesulfonyl chloride was added.
The temperature was raised to 25 to 30 ° C., which was added over time, to 3.5.
Stir for hours. After being poured into cold water, extracted with ether, washed with 5% hydrochloric acid and water in this order, dried over anhydrous magnesium sulfate, and then the ether was distilled off to obtain 114 g of (2-propoxypropyl) methanesulfonate.

95% sodium ethoxide 4 in 345 ml of ethanol
3.3g was added and 98% diethyl malonate 11 with stirring
4g was dripped at 33-36 degreeC over 55 minutes. 3 more
After stirring for 0 minutes, 114 g of (2-propoxypropyl) methanesulfonate was added dropwise at 34 to 38 ° C. over 1 hour. The temperature was raised, and the mixture was refluxed at 80 to 82 ° C for 18 hours. After the completion, it was poured into cold water, extracted with benzene, washed with water, benzene was distilled off, and the residue was distilled under reduced pressure to obtain 100 g of ethyl 4-propoxy-2-ethoxycarbonylethyl valerate (75
~ 115 ° C / 5mmHg).

Then, 87 g of 85% KOH was dissolved in 87 ml of water, and 100 g of the above ethyl 4-propoxy-2-ethoxycarbonylvalerate was added dropwise at 15 to 25 ° C. over 45 minutes to give 90 to
After stirring at 96 ° C. for 2 hours, it was cooled. The liquid temperature was maintained at 20 ° C. or lower, and a solution of concentrated sulfuric acid (138 g) and water (194 ml) was added dropwise over 30 minutes. After stirring at 90 to 95 ° C for 3 hours, the mixture was cooled to room temperature and extracted with ether. After washing the ether layer with saturated saline, the ether was distilled off and the residue was distilled under reduced pressure.
47 g of a fraction of 100 to 130 ° C./5 mmHg was obtained. Benzene was added to this, and washed with a 5% NaOH aqueous solution, and the aqueous layer was washed with 6
After acidifying with N hydrochloric acid (pH = 1) and extracting with ether,
The extract was washed with saturated brine, the ether was distilled off, and 38 g of 4-
Propoxyvaleric acid was obtained.

Next, 10.1 g of LiAlH ₄ was added to 217 ml of dry ether, and the solution of 38 g of _4- propoxyvaleric acid and 44 ml of ether was kept under 10 ° C. with stirring and added dropwise over 3.5 hours. After the dropping, the temperature was raised to 20 to 25 ° C., the mixture was stirred for 3 hours, and then left for 12 hours. 5% Hydrochloric acid aqueous solution was added to make the mixture acidic (pH = 1), extracted with ether, washed with 5% NaOH aqueous solution and saturated saline in this order, and dried over anhydrous magnesium sulfate, and then ether was distilled off. Then vacuum distillation, 109 ~
26 g of (R) -4-propoxypentanol, which is a fraction of 117 ° C./35 mmHg, was obtained.

Reference Example 5 4- (4'-pentyloxypentyloxy) phenol was produced by the following steps.

17 g of 4-pentyloxypentanol and 60 g of pyridine
Dissolve in 2 ml and stir 22.4 g of tosyl chloride at 10 ° C with stirring.
The following was added over 40 minutes. The temperature was raised to 25 ° C. and the mixture was stirred for 3 hours. After the reaction, add cold water and extract with ether, then 5%
It was washed with hydrochloric acid and water in this order, and dried over anhydrous MgSO ₄ . The solvent was distilled off to obtain 31.9 g of (4-pentyloxypentyl) p-toluenesulfonate.

Then hydroquinone 16.1 g, 85% KOH 6.6
g, 30 ml of methanol, and 120 ml of ethanol were added and dissolved. The above-mentioned tosylate body 31.
9 g of ethanol solution was added dropwise over 40 minutes. After the dropping, the temperature was raised to 65 ° C., and the mixture was further stirred for 2 hours. After refluxing for 7 hours, the mixture was cooled and poured into cold water. Hexane extraction, 5% N
It was washed with an aqueous aOH solution and added to the aqueous layer. The aqueous layer was acidified (pH 1) with 6N hydrochloric acid, extracted with hexane and washed with water to give anhydrous M
It was dried over gSO ₄ . The solvent was distilled off to obtain 18 g of a brown liquid. This was purified by silica gel column chromatography (developing solvent ether: hexane = 3: 1), and 4-
8.5 g of (4'-pentyloxypentyloxy) phenol was obtained.

The following IR data was obtained on the product.

IR (cm ^-1 ): 3350, 2960 to 2870, 1510, 1450, 1380, 1230, 1100, 820.

Reference Example 6 4- (4′-propyloxypentyloxycarbonyl) phenol was produced by the following steps.

p-acetoxybenzoic acid 19.7 g benzene 120 ml
23.4 g of phosphorus pentachloride was added little by little to the solution at room temperature with stirring. Then, the mixture was heated under reflux for 4 hours and the solvent was distilled off to obtain 21.5 g of an acid chloride.

Next, 16.0 g of 4-propoxypentanol, N, N-
Dimethylaniline (13.3 g) was dissolved in ether (32 ml), and the above acid chloride (21.5 g) was added dropwise over 40 minutes with stirring at room temperature. After the dropping, the mixture was heated under reflux for 2.5 hours. After the reaction, 80 ml of water was added to dissolve the crystals and the mixture was extracted with ether. The ether layer was washed with 10% sulfuric acid and water in this order, and dried with anhydrous N
It was dried over a ₂ SO ₄ and the solvent was distilled off to obtain 33.9 g of an oily substance. This is subjected to silica gel column chromatography [hexane: isopropyl ether = 2: 1 to 1: 1].
(Gradient)] and the ester form 23.9 g
Got

Next, 23.9 g of the ester compound was dissolved in 80 ml of methanol, and a solution of methanol / aqueous ammonia (28%) = 1/1 was added with stirring. After the reaction, the mixture was extracted with ether, washed with water, and dried over anhydrous Na ₂ SO ₄ . Evaporate the solvent to remove 4-
18 g of (4'-propyloxypentyloxycarbonyl) phenol was obtained. The following IR data was obtained on the product.

IR (cm- ¹ ): 3350, 2970-2870, 1720, 1615, 1590, 1520, 1280, 1170, 1100.

Example 1 5-octyl-2- [4- (4'-octyloxypentyloxy) phenyl] pyrimidine was prepared by the following steps.

4-Octyloxypentanol (7 g), p-toluenesulfonyl chloride (4.34 g), pyridine (1.8 g) and benzene (10 ml) were added, and the mixture was stirred at room temperature for 22 hours under an N ₂ stream. Then hot concentrated NaOH aqueous solution 6.5 in the reaction mixture.
ml was added and stirred for 5 minutes. Then, it was poured into cold 10% hydrochloric acid and extracted with hexane. The hexane layer was washed with cold 5% hydrochloric acid, a saturated NaHCO ₃ aqueous solution, and water in this order, and then dried with anhydrous M
It was dried over gSO ₄ . The solvent was distilled off and treated with an alumina column (hexane) to obtain 6.6 g of (4-octyloxypentyl) p-toluenesulfonate.

Next, 5-octyl-2- (4-hydroxyphenyl) pyrimidine 5.75 g, KOH1.007 g, DMF28
ml was added, and the mixture was stirred at 100 ° C. for 50 minutes. Thereafter, 6.0 g of the above tosylate compound was added, and the mixture was stirred at 100 ° C. for 2.5 hours. After the reaction was completed, it was poured into 500 ml of cold water and extracted with benzene. The benzene layer was dried over anhydrous MgSO ₄ , and the solvent was distilled off. Further treatment with an alumina column (hexane) gave 3.1 g of crystals. This was recrystallized from ethanol to give 5-octyl-2- [4- (4'-
1.62 g of octyloxypentyloxy) phenyl] pyrimidine was obtained. The following IR data and NMR data were obtained for the product.

IR (cm- ¹ ): 2970-2860, 1610, 1590, 1440, 1260.

_{NMR (CDC1 3) δ: 8.5~6.8} (6H), 4.2~2.3 (7H), 2.1~0.6 (37H) ppm.

Examples 2 to 3 The following compounds were synthesized by the same method as in Example 1. The product is shown with IR and NMR data.

-5-decyl-2- [4- (4'-propoxypentyloxy) phenyl] pyrimidine IR (cm- ¹ ): 2970-2860, 1610, 1590, 1440, 1260.

_{NMR (CDC1 3) δ: 8.6~6.8} (6H), 4.2~2.3 (7H), 2.1~0.6 (31H).

-5-nonyl-2- [4- (4'-pentyloxypentyloxy) phenyl] pyrimidine IR (cm- ¹ ): 2970-2860, 1610, 1590, 1440, 1260.

_{NMR (CDC1 3) δ: 8.6~6.8} (6H), 4.2~2.3 (7H), 2.1~0.6 (33H).

Example 4 4- (4'-decyloxyphenyl)
4-Octyloxypentyl benzoate was prepared.

4- (4'-decyloxyphenyl) benzoic acid 3.28
1.97 g of phosphorus pentachloride in 10 ml of benzene
Was added little by little with stirring at room temperature. Then, the mixture was refluxed for 6 hours, and the solvent was distilled off to obtain 3.60 g of acid chloride.

Next, 2.0 g of 4-octyloxypentanol was put into 16 ml of pyridine, and a solution of the above acid chloride in 10 ml of toluene was added dropwise at 2 ° C. After dropping, the mixture was stirred for 7 hours, poured into ice water and acidified with 6N hydrochloric acid, and the generated crystals were separated.
The organic layer was washed with water, 2N NaOH aqueous solution, and water in this order, and dried over anhydrous MgSO ₄ .

The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1), 2.
7 g of crystals were obtained. Further recrystallized from ethanol,
1.2 g of 4-octyloxypentyl 4- (4'-decyloxyphenyl) benzoate was obtained. For products,
The following IR and NMR data were obtained.

IR (cm- ¹ ): 2970-2860, 1720, 1610, 1290, 1200, 1120.

NMR (CDC1 ₃ ) δ: 8.3 to 6.9 (8H), 4.6 to 3.2 (7H), 2.2 to 0.7 (41H).

Example 5 4-octyloxybenzoic acid 4-
(4'-Pentyloxypentyloxy) phenyl was prepared.

2.5 g of 4-octyloxybenzoic acid and 8 parts of thionyl hydrochloride
ml was added and refluxed for 2 hours. Excess thionyl chloride was distilled off to obtain an acid chloride.

Next, a toluene solution of the above acid chloride was added dropwise to a solution of 2.6 g of 4- (4'-pentyloxypentyloxy) phenol in 12 ml of pyridine at 10 ° C or lower over 15 minutes. After dropping, the mixture was stirred at room temperature for 15 hours. After the reaction, the mixture was poured into cold water and extracted with ether. The ether layer was washed with 5% hydrochloric acid, water, 5% NaOH aqueous solution, and water in this order, and dried over anhydrous Na.
Dry with ₂ SO ₄ . The solvent was distilled off and recrystallized from ethanol to obtain 4.4 g of 4- (4'-pentyloxypentyloxy) phenyl 4-octyloxybenzoate.

IR (cm < ^-1 >): 2960-2860, 1730, 1600, 1510, 1470, 1250, 1190, 1070, 760.

Examples 6 to 7 The following compounds were synthesized by the same method as in Example 5.

4- (4'-pentyloxypentyloxy) phenyl 4-decyloxybenzoate IR (cm < ^-1 >): 2970-2850, 1730, 1600, 1510, 1470, 1250, 1190, 1070, 760.

* 4- (4'-dodecyloxyphenyl) benzoic acid 4-
(4'-Pentyloxypentyloxy) phenyl IR (cm < ^-1 >): 2970-2850, 1730, 1600, 1510, 1470, 1250, 1190, 1070, 760.

Example 8 4-octyloxybenzoic acid 4-
(4'-Propoxypentyloxycarbonyl) phenyl was prepared.

4-octyloxybenzoic acid 4.0 g benzene 13 ml
To the solution, 3.40 g of phosphorus pentachloride was added little by little with stirring at room temperature. Then, the mixture was refluxed for 4 hours and the solvent was distilled off to obtain 4.6 g of an acid chloride.

Next, 4.26 g of 4- (4'-propoxypentyloxycarbonyl) phenol was dissolved in 20 ml of pyridine,
A solution of 4.6 g of the above acid chloride in 13 ml of toluene was added dropwise at 3 ° C. Then, it stirred at room temperature for 18 hours. After the reaction
The mixture was poured into ice water and acidified with 6N hydrochloric acid, and the generated crystals were separated. The organic layer was washed with water, a 2N NaOH aqueous solution, and water in this order, and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated, the residue was purified by silica gel column chromatography (chloroform), and recrystallized from ethanol to obtain 4- (4'-propoxypentyloxycarbonyl) phenyl 4-octyloxybenzoate (1.16 g).

IR (cm- ¹ ): 2970-2860, 1730, 1720, 1610, 1270.

_{NMR (CDC1 3) δ: 8.3~6.8} (8H), 4.5~3.1 (7H), 2.2~0.7 (27H) ppm.

Examples 9 to 10 The following compounds were synthesized by the same method as in Example 8.

-4- (4'-propoxypentyloxycarbonyl) phenyl 4-dodecyloxybenzoate IR (cm < ^-1 >): 2970-2860, 1730, 1720, 1610, 1270.

_{NMR (CDC1 3) δ: 8.3~6.8} (8H), 4.5~3.1 (7H), 2.2~0.7 (35H) ppm.

-4- (4'-octyloxyphenyl) benzoic acid 4-
(4'-propoxypentyloxycarbonyl) phenyl IR (cm < ^-1 >): 2970-2860, 1730, 1720, 1610, 1270.

_{NMR (CDC1 3) δ: 8.3~6.8} (12H), 4.5~3.1 (7H), 2.2~0.7 (27H) ppm.

Example 11 Preparation of 5-dodecyl-2- [4- (4-propoxypropyloxy) phenyl] pyrimidine.

15 g of (R) -4-propoxypentanol was dissolved in 50 ml of pyridine and kept at 15 ° C. or lower by cooling with ice, 21.3 g of P-toluenesulfonyl chloride was added, and the mixture was returned to room temperature and stirred for 15 hours. Then, pour the reaction mixture into 500 ml of ice water with stirring, add 5% hydrochloric acid, and add acid (pH =
1-2) and extracted with methylene chloride. The methylene chloride layer was washed with water and dried over anhydrous magnesium sulfate,
The solvent was distilled off to give [(R) -4-propoxypropyl].
14.4 g of P-toluenesulfonate was obtained.

Next, 5-dodecyl-2- (4-hydroxyphenyl)
Pyrimidine 2.5g, 85% KOH 0.49g, N, N
A mixture of 20 ml of dimethylformamide at 100 ° C.
Stir for hours. Then, 2.0 g of the above tosylate compound was added and stirred at 100 ° C. for 5 hours. Cold water after the reaction 25
Pour into 0 ml and extract with isopropyl ether. The isopropyl ether layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was evaporated. It was treated with silica gel column chromatography (developing solvent n-hexane / ethyl acetate = 10/2) and recrystallized from n-hexane to give 5-dodecyl-2- [4- (4-propoxypropyl) phenyl] pyrimidine. 1.77 g was obtained.

Phase transition temperature (℃) Example 12 A polyimide film having a film thickness of 1000 Å was formed on each of the opposing matrix electrodes formed of crossed strip ITO (5 of polyamic acid resin composed of a combination of pyromellitic anhydride and 4,4′-diaminodiphenyl ether). Was formed by coating a wt% N-methylpyrrolidone solution and heating and ring closing reaction at a temperature of 250 ° C., and rubbing the surfaces of this polyimide film so as to be parallel to each other to prepare a cell having a cell thickness of 1 μm. did.

Then, the following composition A was injected into the above-mentioned cell under an isotropic phase by a vacuum injection method and sealed. Then, a SmC ^* liquid crystal cell was prepared by slow cooling (1 ° C./hour).

Liquid crystal composition A: A crossed Nicol polarizer and an analyzer were arranged on both sides of the liquid crystal cell, and signals having the waveforms shown in FIGS. 4 and 5 were applied between the opposed matrix electrodes. At this time, the scanning signal is an alternating waveform of +8 volts and -8 volts shown in FIG. 4 (a),
The writing information was +4 volt and -4 volt, respectively. Further, one frame period is set to 30 m · sec.

As a result, even when the liquid crystal element was subjected to the memory drive type time division drive described above, a normal moving image display was obtained without any inversion of the written state.

Example 13 A liquid crystal element was produced in the same manner as in Example 12 except that the liquid crystal composition B described below was used instead of the liquid crystal used in Example 12, and the same method as that used in Example 12 was applied to the liquid crystal element. As a result of displaying a moving image by the same driving method, no inversion phenomenon was observed on the screen in any of the examples.

Liquid crystal composition B: Comparative Example 1 The following comparative liquid crystal B ′ was prepared by omitting the optically active substance represented by the above general formula (I) in the liquid crystal composition B used when preparing the liquid crystal device of Example 13. A liquid crystal element was prepared using the comparative liquid crystal. This liquid crystal element was driven by the same method as described above, but a normal moving image was not displayed due to the inversion phenomenon.

Comparative liquid crystal B ':

[Brief description 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 view showing an electric signal applied to the matrix electrode, FIGS. 5 (a) to (d) are explanatory views showing a waveform of a voltage applied between the matrix electrodes, and FIG. It is explanatory drawing of the time chart showing the electric signal applied to the liquid crystal element of this invention. 11a, 11b ... 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 ₁ , S ₂ , S ₃ , ・ ・ ・) …… Scan electrode group, 33 …… (I ₁ , I ₂ , I ₃ , ...) ... Signal electrode group.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 69/94 9279-4H C07D 239/26 8615-4C C09K 19/12 7457-4H 19/20 7457 −4H 19/30 7457-4H 19/34 7457-4H 19/46 7457-4H 19/48 7457-4H // G02F 1/13 500 (72) Inventor Masataka Yamashita 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Kazumi Kazuharu 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (3)

[Claims] 1. A general formula (I) [In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms, and C ^* represents an asymmetric carbon atom. l is 0 or 1, and when l = 1, m and n are 0 or 1. A is (However, R ¹ represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms, Respectively Where p, q and r are 0 or 1 and p + q + r ≧ 1
The optically active hydroxyvaleric acid derivative represented by 2. General formula (I) [In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms, and C ^* represents an asymmetric carbon atom. l is 0 or 1, and when l = 1, m and n are 0 or 1. A is (However, R ¹ represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms, Respectively Where p, q and r are 0 or 1 and p + q + r ≧ 1
The liquid crystal composition is characterized by containing at least one kind of an optically active hydroxyvaleric acid derivative represented by the formula (1). 3. General formula (I) [In the above general formula, R represents an alkyl group having 1 to 18 carbon atoms, and C ^* represents an asymmetric carbon atom. l is 0 or 1, and when l = 1, m and n are 0 or 1. A is (However, R ¹ represents an alkyl group or an alkoxy group having 4 to 18 carbon atoms, Respectively Where p, q and r are 0 or 1 and p + q + r ≧ 1
The liquid crystal element is characterized by using a liquid crystal composition containing at least one kind of the optically active hydroxyvaleric acid derivative represented by the formula [1].