JPH0344367A - Thioester derivative of optically active propionic acid, its intermediate, production thereof, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is 1-18C alkyl, alkoxy, alkoxycarbonyl, alkanoyloxy, etc. which may be substituted by halogen or CN; R<2> is 1-18C alkyl; m is 0 or 1; rings A and B are phenylene, cyclohexylene, formula II, etc.; Z is COO, OCO, CH2O, OCH2 or single bond; ring C is phenylene, group expressed by formula III, etc.; C* indicates asymmetric carbon atom). EXAMPLE:S-Butyl (S)-2-{4-[4-(4-octyloxyphenyl)benzoyloxy]phenyl}propanethioate. USE:A liquid crystal compound. PREPARATION:The compound expressed by formula I is obtained by a method for converting a compound expressed by formula IV into an acid chloride and then reacting the resultant acid chloride with a compound expressed by formula V (new substance), etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel optically active compound, an intermediate thereof, a method for producing the intermediate, a liquid crystal composition, and a liquid crystal display element.
In particular, the present invention relates to ferroelectric liquid crystal display materials with excellent responsiveness and memory properties, and raw materials thereof.

[Prior art]

Liquid crystal display elements are currently widely used due to their excellent features (low voltage operation, low power consumption, thin display capability, and can be used in bright places without straining the eyes). However, in the most common TN type display system, CR
Compared to light-emitting display systems such as T, the response is extremely slow and there is no memorization of the display (memory effect) when the applied electric field is turned off. There are many restrictions on the application to video screens such as televisions, which require a high resolution, and it has not been possible to say that it has been successfully applied.

Recently, Mayer et al. reported a display method using ferroelectric liquid crystal, which has a high-speed response and memory effect that is 00 to 1000 times faster than that of the TN type, and has been promoted as the next generation liquid crystal display element. Currently, active research and development is underway.

The liquid crystal phase of the ferroelectric liquid crystal belongs to the tilted chiral smectic phase, but for practical purposes, the chiral smectic C (hereinafter abbreviated as Sc) phase, which has the lowest viscosity, is the most desirable. .

Many liquid crystal compounds exhibiting the Sc' phase have already been synthesized and studied, but the conditions for use as ferroelectric display elements are: (a) Sc' phase in a wide temperature range including room temperature;
(b) In order to obtain good orientation, Sc”
It has an appropriate phase series on the high temperature side of the phase, and its helical pitch is large; (c) it has an appropriate tilt angle;
D) It is preferable that the viscosity is low, and (main) that the spontaneous polarization is large to some extent, but there is no known material that satisfies these requirements alone.

For this reason, it is used as a composition exhibiting the Sc'' phase.

Smectic C (S
c) A common method is to add a chiral dopant made of an optically active compound to a parent liquid crystal exhibiting a phase.

Although it is not necessary for the optically active compound used as a chiral dopant to exhibit an Sc'' phase or a liquid crystal phase, when it is added to a base liquid crystal to form an Sc'' composition,
■It is particularly important that even a small amount of addition induces a sufficiently large spontaneous polarization.

Although many Sc'' compounds or optically active compounds have been synthesized for this purpose, none of them can satisfy all of the above conditions.

In addition, as a compound similar to the compound (1) of the present invention, there can be mentioned a compound already disclosed by the present inventors in Japanese Patent Application No. 194449/1983, but this compound also has an induced effect when added as a chiral dopant. It was desirable to further increase the spontaneous polarization.

[Problem to be solved by the invention]

As mentioned above, conventional Sc'' compounds or optically active compounds have a characteristic of spontaneous polarization or helical pitch.
It never shows sufficient performance, and the patent application
Further improvement in performance has been desired for the material shown in No. 3-194449, and improvements have been desired in order to provide a liquid crystal material with high-speed response and good alignment.

The problem to be solved by the present invention is to provide an optically active compound that exhibits large spontaneous polarization and low viscosity when used in a liquid crystal material, thereby making it possible to provide a ferroelectric liquid crystal display material capable of high-speed response. There is a particular thing.

[Means for solving problems]

In order to solve the above problems, the present invention provides the following general formula (1
) is provided.

... (1) In the formula, R1 represents an alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl, alkoxyalkyl or alkoxyalkoxy group having 1 to 18 carbon atoms which may be substituted with a halogen or cyano group, and Rt is a carbon Represents a linear or branched alkyl group having a number of 1 to 18.

Represents a fluorine, chlorine, or CN group substituted on a ring.

Z represents COO1OCO, C11□0.0CR1 or a single bond.

is preferred.

C* represents an asymmetric carbon having the (S) or (R) configuration.

The present invention also provides an optically active compound represented by general formula (II), which is a synthetic intermediate for the novel optically active compound represented by general formula (1).

In the formula, X represents a hydrogen atom or 2 of a 1,4-phenylene group.
Represents a fluorine atom, chlorine atom, or cyano group substituted at the position or 3-position. C" represents an asymmetric carbon atom having an (S) or (R) configuration, and RZ represents a linear or branched alkyl group having 1 to 18 carbon atoms.

The present invention also provides a liquid crystal composition using the novel compound of the above general formula (I), a liquid crystal display element using the same, and a method for producing the compound of the above general formula (II).

To produce the compound of general formula (I), the following general formula (Vl
) is the acid chloride (■). ) This represents a compound represented by the following general formula (II) in the presence of a basic substance such as pyridine, where X is a hydrogen atom or 2 of a 1,4-phenylene group.
Represents a fluorine, chlorine or cyano group substituted at the position or 3-position, and C" R2 represents the same as in general formula (1).)
Alternatively, the compounds of general formulas (Vl) and (II) can be directly reacted with dicyclohexylcarbodiimide (DC
Esterification may be carried out using a condensing agent such as C).

Here, the compound of general formula (It) is an optically active propionic acid derivative represented by general formula (III) (wherein R3
represents a lower alkyl group, and C'' represents the above general formula (1
) (This compound has the same meaning as
94449) and a thiol represented by the general formula (IV) in the presence of a condensing agent, or its-R2... (IV) (wherein R2 is the above general formula (1) )) Alternatively, by converting the compound of general formula (I [I) into an acid chloride with thionyl chloride etc. and reacting it with 1,000-ol of general formula (TV), the compound of general formula (V) can be prepared. It can be obtained by obtaining an optically active propionic acid thioester derivative represented by and dealkylating it using a dealkylating agent such as boron tribromide.

In formula (II), R"C" has the same meaning as that of general formula 2 (H). The compound of general formula (1) of the present invention is produced as described above, but the individual compounds belonging thereto Specific compounds and individual specific intermediates belonging to the above general formula (II) etc. can be confirmed by means such as melting point, phase transition temperature, infrared absorption vector, magnetic resonance spectrum, mass spectrometry, etc.

General formula (1) according to the present invention produced in this way
The phase transition temperatures of representative compounds are shown in the table below.

In addition, in the table, Cr indicates crystalline phase, Sa indicates smectic A phase, and S
x represents a chiral smectic phase of unknown attribution, and the parentheses indicate that the phase is monotropic. The book shows that the phase is confirmed to exist in a monochromatic pink upon rapid cooling, but the transition temperature cannot be measured due to crystallization.

(Margins below this page) Some compounds of the general formula (I) of the present invention exhibit a liquid crystal phase when used alone, but they do not exhibit a Sc" phase over a wide range, so they are not suitable for use alone. When used as a composition, especially as a ferroelectric liquid crystal display element, it can be used as a Sc'' liquid crystal composition by adding it as part or all of the chiral dopant in the Sc liquid crystal composition with low viscosity. is effective.

5cl doped with the compound of general formula (1) of the present invention
Examples of Sc compounds to be used as precepts include:
Examples include phenylbenzoate compounds represented by the following general formula (A) and pyrimidine compounds represented by the general formula (B).

(In the formula, R1 and Rh are linear or branched alkyl groups,
Represents an alkoxyl group, an alkoxycarbonyl group, an alkanoyloxy group, or an alkoxycarbonyloxy group, and may be the same or different.

) (wherein R" b is the same as in the above general formula A) Furthermore, a compound represented by the general formula () () () general formula (C) can also be used for the same purpose.

(In the formula, R"Rh is the same as in general formula A, or represents a halogen substituted product thereof, and may be the same or different. Za is -COO--OCO--
C) 120-, -0CHz, -CHzCHz-,
-CmiC- or a single bond. ) Furthermore, for the purpose of expanding the temperature range of the Sc phase to a high temperature range, a tricyclic compound represented by the general formula (D) can be used.

(In the formula, R"R' is the same as in the general formula A, and may be - or different, and z" and zb are the same as Za in the general formula (C) above, and are the same. Although it is effective to mix these compounds and use them as a Sc liquid crystal composition, it is sufficient that the composition exhibits an Sc phase, and individual compounds do not necessarily have a Sc phase. There is no need to indicate.

The general formula (1) of the present invention of the Sc liquid crystal composition thus obtained is
) and, if necessary, other optically active compounds as chiral dopant, it is possible to easily obtain a liquid crystal composition that exhibits the Sc phase over a wide temperature range including room temperature.

A liquid crystal compound consisting of a compound having an optically active group of the general formula (1) of the present invention, or a liquid crystal composition obtained by doping the same into another Sc compound or Sc liquid crystal composition, has two transparent glass electrodes. By enclosing a thin film of about 1 to 2 μm in between, it can be used as a display cell. In order to obtain good contrast, uniformly oriented monodomains are required. Many methods have been tried for this purpose, but as a liquid crystal material, isotropic liquid phase (N) → chiral nematic phase (N") [phase] smectic A phase (SA) → chiral nematic C phase (Sc It is known that a material exhibiting a phase series of ``)'' and having a large helical pinch in the N0 phase and the Sc'' phase, especially the N'' phase, exhibits good orientation. In order to increase the helical pitch, it is sufficient to mix appropriate amounts of chiral compounds whose twist directions are opposite to each other, but in this case, the spontaneous polarization
Care must be taken not to cancel each other out.

In the compound of the bifurcated formula (I), when both R' and R'' are optically inactive groups, when the absolute configuration of the C chain is (S), the direction of the induced helical pitch is to the left. Yes, the polarity of spontaneous polarization is ■ (a well-known ferroelectric liquid crystal (S)
-2-methylbutyl P-decyloxybenzylidene aminocinnamate (DOBAMBC) is defined as O). Therefore, as an optically active group, it may be used in combination with an optically active compound whose induced helical pitch is in the right direction and its spontaneous polarization is in the form of ■. Furthermore, in the -M formula (I), by selecting the group (i) or (11) above as R1, it is also possible to adjust the pitch to be long while strengthening the spontaneous polarization. Also, a group with the same direction of helical pitch is R'
In this case, the helical pitch induced by the obtained compound is short, and such a compound is
It can be used for adjusting the helical pitch, or by adding it to ordinary nematic liquid crystals to suppress reverse domains, or for use in STN liquid crystals.

〔Example〕

The present invention will be specifically explained with reference to Examples below.
Of course, the gist and scope of the present invention are not limited to these examples.

The structure of the compound is determined by nuclear magnetic resonance spectrum (NMR).
, and confirmed by infrared absorption spectrum (IR) and mass spectrum (MS). The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (D
SC) was used in combination. (KBr) in IR represents measurement by tablet molding, and (IIeat) represents measurement by liquid film. (CDCl2:+) and (CCL) in NMR
represents a solvent, S represents a singlet, d represents a doublet, t represents a triplet, q represents a quartet, m represents a multiplet, broad represents a broad absorption, and J represents a coupling constant. M'' in MS represents the parent peak, and the number in parentheses represents the relative intensity of that peak. Also, temperature is in °C. All percentages in the composition are percentages by weight.

Example a 1 (S)-2-(4-hydroxyphenyl)
Synthesis of S-butyl propanethioate 1-a Synthesis of S-butyl (S)-2-(4-methoxyphenyl)propanethioate (S) 540 mg of 2-(4-methoxyphenyl) propanoic acid (83% ee) and chloride After heating 5 ml of thionyl for 10 minutes, thionyl chloride was removed under reduced pressure. Butane-1-thiol 0.7 mf, dichloromethane 3 m
j2 and pyridine 0.81II2 were added at room temperature and stirred for 1 hour. Butanethiol and dichloromethane were removed under reduced pressure, treated with water, extracted with ether, and purified by thin layer chromatography (silica gel, hexane/ethyl acetate = 5/1) to yield (S)-2-(4-methoxyphenyl). 505 mg of S-butyl propanethioate was obtained.

Identification data is shown below.

Oily substance Boiling point 110'C10, 5 plates Hg (α)
+82.1° (cm1.05. CHCl:+)I
R(IIeat) 2950.1680 (C=O),
1610.1510.1460゜1250, 1180
．． 1035.950.830.760 cm-''l(
N? lR(CCP, ,) δQ,9 (t, J=6H
z, 3H), 1. Q~1.6 (III, 4H), 1
．． 4(d, J=7Hz, 3H), 2.75(t, J=
6) 1z.

311), 3.7 (q, J=7Hz, IH), 3.
75 (s, 38), 6.7 (d.

J=9Hz, 21(), 7.1(d, J=91(z,
2) 1) MS m/z: 252 (M”, 4.5
), 135 (100) Elemental analysis: C14112
Calculated value as ゜O□S: C, 66, 63, H, 7,
99, S, 12.71! Actual value: C, 66.5
3; H, 8,15; S, 12.66%1=b
Synthesis of S-butyl (S)-2-(4-hydroxyphenyl)propanethioate (S)-2-(4-methoxyphenyl)propanethioate S-butyl 490 mg dichloromethane 2.5 + nj2
The solution was added to a boron tribromide jig at -50°C and stirred for 30 minutes. Add saturated saline at -78°C, extract with ether, and purify by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) to (S)-2-
410 μm of S-butyl (4-hydroxyphenyl)propanethioate (yield: 100%) was obtained.

Identification data is shown below.

Oily substance Boiling point 130°C / 0. 6mmHg
(α) +83.9° (cm0.99.CH
C l s) IR (IIeat) 3450
(O)l), 2980, 2940. 166
0 (C=0).

1615, 1610, 1440, 1370, 1220,
1000,950830,130+ 540 am-
''H NMR (CDCl z) δ 0.
9 (t.J=6Hz, 311), 1.0~1,
6 (III.4H), 1.5 (d, J=6Hz.3
H), 2.8(t, J=7t(z.

2H), 3.8 (q, J=6Hz, IH), 5
．． 2-(s.lH), 6.8(d.

J=9Hz, 2H), 7.15(d, J=9Hz,
2H) MS re/z: 23B (M”
, 13.4), 121 (100) Mass spectrometry using high-resolution MS: Calculated value as C+J+aO□S: 238.1026; Actual value: 238.
1024 Example 2 Synthesis of (S)-2-(2-(6-hydroxynaphthyl))]S-propanethioic acid 2-a (S)-2-(2-(6-methoxyfer)]]S-propanethioic acid Synthesis of -butane e0 eO 1.3 g of commercially available (Aldrich) (S)-2-(2-(6-medoxynaphthyl))propanoic acid, butane-1-
1 ml thiol, polyphosphoric acid ethyl ester (PPE)
)-chloroform solution 15 m Il (Biochem
.

Biophys, Acta, 80, 1 (196
4); 5ynthesis.

1982, 134; Bull, CheIIl,
Soc, Jpn, 55, 2303 (1982)
, ) was reacted at room temperature for 2 hours, treated with an aqueous sodium bicarbonate solution, and extracted with ether.

Column chromatography (Wako gel C-200゜2
0mmφX300mm, hexane/ethyl acetate = 5/1
), 1.7 g of S-butyl (S)-2-(2-(6-medoxynaphthyl))propanethioate (yield 100%)
) was obtained.

Identification data is shown below.

Melting point 45°C (α) + 121.2° (C・i, 23.CHC
fx) IR (KBr) 1295.1690 (C=O
), 1605.1440.1270°1230, 11
? 5.1030.990.950.860.825゜6
50+ 480 cm-' HNMR (CDCl, J) δ0.86 (t, J
=6.4Hz, 3H).

1.1 = 1.7 (+n, 4H), 1.60 (d
, J=7.2Hz, 3H), 2.83(t, J=7
．． 0Hz, 2H), 3.90(s, 3H), 4
．． 00 (q, J=7.0Hz 1B) 7.0~7.
8 (III, 6) 1) MS m/z: 302
(M”, 12.8), 185 (10
0) Elemental analysis' Calculated value as C+aHzOzS:
C, 71,49; H,? ,33,S,10
．． 60χ actual value: C, 71,75; H, 7,42
; S , 10.63 $2-b (S)-2-(
2-(6-hydroxynaphthyl))propanethioic acid S-
Synthesis of butyl (S)-2 (2-(6-medoxynaphthyl))] Add a 71M solution of boron tribromide in dichloromethane 9-1 to a 10mf dichloromethane solution of 1.6 S-butyl propanethioate at -50°C. After adding, the temperature was raised to 0°C and heated to 30°C.
The mixture was stirred for a minute. Add saturated saline at -78"C, ether extraction, column chromatography (Wakogel C-20
0.20 mm φ x 300 stamps, hexane/ethyl acetate = 4/
1) (S)-2-(2-(6hydroxynaphthyl))] S-butyl propanethioate 1.5g Yield 98%
) was obtained.

Identification data is shown below.

Melting point 102°C IR (KBr) 3480 (OH), 2990.2
950.1675 (C=0).

1630, 1610.1460.1395.1200.
1000.960°860, 830.760.590.
480 cm-''tlNMR (CDCf3) δ0
．． 86 (,t, J=6.3Hz, 3H).

1.1-1.7 (III, 4H), 1.59 (d, J
=7.2Hz, 38), 2.82(t, J=6.8H
z, 2H), 3.99 (q, J=7.2tlz, LH
), 5.47 (s, LH) 6.9-7.8 (III
, 6H) MS m/z: 288 (M”, 12
．． 3), 171 (100) Elemental analysis: C+Jz
Calculated value as oO□S: C, 70, 80,; H,
6,99; S, 11.12 Z actual value: C, 7
0,82, H, 6,98, S, 11.08 Z Example 3 (S)-2-(4-(4-(4-octyloxyphenyl)benzoyloxy]phenyl)propanethioic acid S-
Synthesis of butyl (compound of Table I No. 1) 4'-octyloxybiphenyl-4-carboxylic acid chloride lσO
1 and 145 ml of S-butyl (S)-2-(4-hydroxyphenyl)propanethioate obtained in Example 1 were dissolved in 61 ml of dichloromethane, 2 ml of pyridine was added, and the mixture was reacted under reflux for 6 hours.

After cooling, ether and dilute hydrochloric acid were added, and the organic layer was washed with an aqueous sodium bicarbonate solution, water, and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography to obtain 168 cm of white crystals of the title compound. (yield 73%)
, and further purified by recrystallization from ethanol, and its phase transition temperature was measured. The results are shown in Table 1.

Identification data is shown below.

2.82 (t, 2H, CtlzS) 1.13
~2.10 (III, 19H.

1.07 (III, 6H, other CH3) IR:
1780. 1?10. 1600. 1580.
1515. 1310°1260, 1220. 11
60. 1035. 995. 845°760c
m-' Examples 4 to 6 In the same manner as in Example 3, N in Table 1
(12 (Example 4), Na5 (Example 5), Nα4
Each compound of (Example 6) was synthesized. The respective phase transition temperatures are summarized in Table 1.

Identification data is shown below.

Compound of Na, 2 NMR: 6.90-8.33 (
III, 12H.

mouth~1.07 (III, 61L other CH3) IR
: 1730. 1680. '1600. 129
0. 1270. 1210°1170.1080,9
50,830.770 cl'Na3 compound NMR
: 6.83 ~ 8.27 (III, 108°■ ~ 1.03 (III, 6H, other CIl + 1) I
R: 1720, 1690, 1600, 1310°1
210.1170,1140,1070°760c
m-' No. Compound 4~8.40 6.86 NMR: 1260 1250°1010.895,845 (III, 14H.

~1.07 (+++, 6H, other CH: 1) IR
:1725. 1680. 1600. 1290.
1280. 1200°1150.1080,955,
900,830,765cm-'Example 7 (Sc“
Preparation of Composition and Creation of Display Element) A base liquid crystal exhibiting an Sc phase having the following composition was prepared.

This composition has a Sc phase below 6865°C and a temperature of 73.5°C.
The SA phase was shown below, the N phase was shown below 83.5'C, and the ■ phase was shown above the temperature. Moreover, its melting point was 13°C.

Sc" composition was prepared by adding 10% of the compound shown in Table I No. 1 to this base liquid crystal. This composition was heated at 60°C.
Sc" phase below, SA phase below 78.5°C, 83.5
It showed N0 phase below °C. This m paraboloid is subjected to orientation treatment (polyimide coating-rubbing) with a spacing of approximately 2μ.
A display cell was prepared by filling the space between two glass transparent electrodes of M and slowly cooling it from the ■ phase to room temperature to orient the Sc'' phase.

The orientation was very good.

This cell has an electric field strength of 10 VP-Pl pm at 25°C.
.

When a 50H2 rectangular wave was applied and the electro-optic response speed was measured, it showed a high-speed response of 500 μsec.

Furthermore, the contrast was also very good.

[Effects of the Invention] When the compound of the formula (1) of the present invention is added to and mixed with a base Sc liquid crystal compound or composition as all or a part of a chiral dopant to form an Sc'' liquid crystal composition, , it is possible to induce large spontaneous polarization with the addition of a small amount, and with such a composition, the viscosity can be kept low, and the reaction time is several hundred microseconds, which is less than 1/100 of that of conventional nematic liquid crystals. This makes it extremely useful as a material for liquid crystal devices.

Furthermore, the compound of the present invention can be easily produced industrially by the production method provided by the present invention. Furthermore, it is colorless itself and has excellent chemical stability against light, water, heat, etc., making it very practical.

Claims (1)

[Claims] (1) An optically active propionic acid thioester derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 is an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an alkoxycarbonyl group, which is unsubstituted or has a halogen atom or a cyano group substituent, represents an alkanoyloxy group, an alkoxyalkyl group, or an alkoxyalkoxy group, R^2 represents a linear or branched alkyl group having 1 to 18 carbon atoms, m represents 0 or 1, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ each independently ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Tables, etc. are available. Yes▼
represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* represents an asymmetric carbon atom in the (R) or (S) configuration. ) (2) The optically active propionic acid thioester derivative according to claim 1, wherein m is 0. (3) The optically active propionic acid thioester derivative according to claim 2, wherein ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (4) The optically active propionic acid thioester derivative according to claim 3, wherein ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (5) The optically active propionic acid thioester derivative according to claim 4, wherein R^1 is an alkoxy group having 1 to 18 carbon atoms. (6) The optically active propionic acid thioester derivative according to claim 5, wherein R^2 is C_4H_9. (7) R^1 is C_8H_1_7O, and C^* is (
The optically active propionic acid thioester derivative according to claim 6, which has the S) configuration. (8) The optically active propionic acid thioester derivative according to claim 2, wherein ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (9) The optically active propionic acid thioester derivative according to claim 8, wherein ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (10) The optically active propionic acid thioester derivative according to claim 9, wherein R^1 is an alkoxy group having 1 to 18 carbon atoms. (11) The optically active propionic acid thioester derivative according to claim 10, wherein R^2 is C_4H_9. (12) The optically active propionic acid thioester derivative according to claim 11, wherein R^1 is C_8H_1_7O and C^* has the (S) configuration. (13) The optically active propionic acid thioester derivative according to claim 1, wherein m is 1. (14) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
14. The optically active propionic acid thioester derivative according to claim 13, which has a chemical formula, table, etc.▼. (15) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
15. The optically active propionic acid thioester derivative according to claim 14, which has a chemical formula, table, etc. (16) The optically active propionic acid thioester derivative according to claim 15, wherein Z is a single bond. (17) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
17. The optically active propionic acid thioester derivative according to claim 16, which has a chemical formula, table, etc.▼. (18) The optically active propionic acid thioester derivative according to claim 17, wherein R^1 is an alkoxy group having 1 to 18 carbon atoms. (19) The optically active propionic acid thioester derivative according to claim 18, wherein R^2 is C_4H_9. (20) The optically active propionic acid thioester derivative according to claim 19, wherein R^1 is C_8H_1_7O and C^* has the (S) configuration. (21) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
The optically active propionic acid thioester derivative according to claim 13, which has a chemical formula, table, etc. ▼. (22) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
22. The optically active propionic acid thioester derivative according to claim 21, which has a chemical formula, table, etc.▼. (23) The optically active propionic acid thioester derivative according to claim 22, wherein Z is a single bond. (24) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ mathematical formulas,
24. The optically active propionic acid thioester derivative according to claim 23, which has a chemical formula, table, etc.▼. (25) The optically active propionic acid thioester derivative according to claim 24, wherein R^1 is an alkoxy group having 1 to 18 carbon atoms. (26) The optically active propionic acid thioester derivative according to claim 25, wherein R^2 is C_4H_9. (27) The optically active propionic acid thioester derivative according to claim 26, wherein R^1 is C_8H_1_7O and C^* has the (S) configuration. (28) The optically active propionate derivative intermediate according to claim 1, which is an optically active propionate derivative represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, ▲There are mathematical formulas, chemical formulas, tables, etc.)
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where X is a hydrogen atom or 2 of a 1,4-phenylene group.
It represents a fluorine, chlorine or cyano group substituted at the position or the 3-position, and R^2 and C^* represent the same as in the general formula (I) of claim 1. ) (29) An optically active propionic acid derivative represented by the following general formula (III) and a thiol represented by the following general formula (IV) are reacted in the presence of a condensing agent, or the following general formula (
After converting the compound III) into an acid chloride, the compound is reacted with a thiol of the following general formula (IV) in the presence of a base to form the following general formula (V).
Claim 28, characterized in that the optically active propionic acid thioester represented by is further dealkylated.
A method for producing an intermediate of an optically active propionic acid thioester derivative represented by the general formula (II). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) (In the formula, R^3 is a methyl group, Represents a lower alkyl group such as an ethyl group, ▲ has a mathematical formula, chemical formula, table, etc. ▼ represents the same as that of general formula (II) in claim 28, and R^
2. C^* represents the same thing as the general formula (I) of claim 1. ) (30) At least one optically active propionic acid thioester derivative of general formula (I) according to claim 1.
A liquid crystal composition containing seeds. (31) The method according to claim 30, wherein at least one of the optically active propionic acid thioester derivatives of general formula (I) according to claim 1 is the optically active propionic acid thioester derivative according to any one of claims 2 to 27. liquid crystal composition. (32) The liquid crystal composition according to claim 30 or 31, which exhibits a chiral smectic C phase. (33) A liquid crystal display element using the liquid crystal composition according to any one of claims 30 to 32.