JPH0356454A - Optically active compound, its production, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> is 1-20C alkyl, etc,; A, B and C are group of formula II, III, IV, etc,; m is 0 or 1; R<2> is 1-15C alkyl, etc,; Z1 and Z2 are COO, OCO, CH2O, CH2CH2, etc,; * represent asymmetric C having R or S configuration). EXAMPLE:4-Decyloxybenzoic acid 4-[(R)-cyano(pentanoyloxy)methyl]-phenyl ester. USE:Useful as a material for a liquid crystal display element, especially a ferroelectric liquid crystal display material having excellent response and memory property and its raw material. PREPARATION:The objective compound of formula I can be produced by reacting an aldehyde of formula V (R<1> is 1-20C alkyl, alkoxy, alkoxycarbonyl, etc,; A, B and C are group of formula II, III, VI, etc.] with trimethylsilyl cyanide in the presence of a lewis acid and an optically active diol and reacting the resultant optically active cyanhydrin derivative of formula VII with a carboxylic acid of formula R<2>COOH.

Description

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

[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 were many restrictions on the application to video screens such as those on televisions, which required a high resolution, and it could not be said to be suitable. Recently, Mayer et al. reported a display method using ferroelectric liquid crystal, which has a high-speed response 100 to 1000 times faster than the TN type and a memory effect, so it is expected to be the next generation of liquid crystal display elements, and currently, Research and development is actively 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. ．． Sc*
Many liquid crystal compounds that exhibit a phase have already been synthesized and studied, but the conditions for using them as ferroelectric display elements are (a) exhibiting an Sc* phase in a wide temperature range including room temperature; ) In order to obtain good orientation, it must have an appropriate phase series on the high temperature side of the Sc' phase and a large helical pitch, (c) it must have an appropriate tilt angle, and (2) it must have low viscosity. (e) Spontaneous polarization is large to some extent;
are preferable, but nothing that satisfies these alone is known.

For this reason, a liquid crystal composition exhibiting the Sc" phase (hereinafter abbreviated as Sc' liquid crystal composition) is used.Sc*liquid crystal composition tc
There are two main methods for preparing liquid crystal compounds: a method of mixing a liquid crystal compound exhibiting an Sc' phase (hereinafter abbreviated as an SC'' liquid crystal compound), and a method of mixing a liquid crystal compound exhibiting an optically inactive S phase (hereinafter referred to as a liquid crystal compound). There is a method of adding an optically active compound or compound as a chiral dopant to a liquid crystal composition (abbreviated as "Kaimono"), but since the SC liquid crystal composition has a lower viscosity than the Sc* liquid crystal composition, the latter method is recommended. is suitable for high-speed response and is common.Chiral dopants do not necessarily need to exhibit Sc' phase or even liquid crystallinity, but do not significantly lower the transition point when added to Sc liquid crystal compositions. Preferably, a substance that can induce a sufficiently large spontaneous polarization by adding as little as possible is advantageous in reducing the viscosity of the SC liquid crystal composition and increasing the response speed. In order to construct such a chiral dopant, the optically active compounds known so far are not sufficient, and compounds that can exhibit stronger spontaneous polarization have been desired.

In order to exhibit strong spontaneous polarization, the asymmetric center and dipole in the compound must be as close as possible to the liquid crystal central skeleton (core), and the stronger the dipole is, the better. Already known. An example of a group that exhibits a strong dipole moment is a cyano group, but it is extremely difficult to connect it directly to an asymmetric center and close to the core; It was used as a raw material. (12th
Proceedings of the International Society of Liquid Crystals, 1988), and no compounds with the asymmetric center closer to the core were known.

[Problem to be solved by the invention]

As mentioned above, when conventional compounds are used as chiral dopants, the spontaneous polarization that they can induce is not large enough, and it has been desired to improve this in order to obtain Sc* liquid crystal compositions with high-speed response. ．． The problem to be solved by the present invention is to provide a novel optically active compound containing a cyano group that can induce sufficiently large spontaneous polarization even when added in a small amount as a part of a chiral dopant, and a method for combining the same. It is an object of the present invention to provide a ferroelectric liquid crystal assembly and a liquid crystal display element capable of high-speed response using the present invention.

[Means to solve the problem]

In order to solve the above problems, the present invention has the following general formula (I)
An optically active compound having a cyano group as shown in the following is provided.

(In the formula, R1 is an alkyl group having 1 to 20 carbon atoms, or any one or 2 to 3 non-adjacent monoCl in this alkyl group, +- is unsubstituted or -O-O
0 0 or one CH=N-, and any 1 to 2 Y. CH! are unsubstituted or substituted with 101, and Yl+Y2 is Y2 independently}l, F, Cj! ,CHx, Ch,
QC}lx, CNO)It', and when an asymmetric carbon is generated by substitution, the absolute configuration of the asymmetric carbon is at least one of (I?), (S), and any CH. , Clj is unsubstituted or substituted with CF 1CF , and X is independently unsubstituted or substituted with -C= or -N=,
-F, -Cl, -CH3. -CN. -CF
3 or -OCH 3, and any 1 to 2 CH2
are unsubstituted or independent two -Cl. - is unsubstituted or substituted with -0- or -S-, any one H
1 is unsubstituted or substituted with -εXI-, and XI is -F.
-Cf, -CH1-CN, -CF. or -OCO, and 2 and Zz each independently represent coo. oc
o, represents a single bond, m represents O or 1, Rz is any one of the alkyl groups having 1 to 15 carbon atoms or 2 to 3 non-adjacent CII2 are unsubstituted or substituted with 101 and any 1 to 3 Ct+Z are unsubstituted Clh
FCJ! or each independently one CH-, -CH-, -CH, the absolute configuration of the asymmetric carbon is at least one of (R), (S), and C゛ is (R) or (S). ) represents an asymmetric carbon atom with the configuration. ) In the above, R1 is preferably an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkoxycarbonyl group, or an alkanoyloxy group. It is also preferable to represent .chi.2 and x3 represent F, CN, or H, and it is particularly preferable that at least one of them is H.

Also, 2. and Z2 are COO, OCO, CHz
Particularly preferred are O 2 , OCHz 2 or a single bond.

Further, Rt is particularly preferably a linear or branched alkyl group that may be optically active, or an optically active group represented by the following general formula (If).

In the formula, 42 and m each independently represent an integer of 0 to 5, particularly preferably f = m = o, and Rff represents a carbon number of 1 to 5.
In the alkyl group of 10, C1 represents an asymmetric carbon having the (R) or (S) configuration.

The present invention also provides a liquid crystal display. The liquid crystal assembly according to the present invention is represented by the general formula (I).
In particular, for ferroelectric liquid crystal displays, it is preferable that at least one compound of the general formula (I) be contained in the host liquid crystal exhibiting the Sc phase, which is the main component. Sc" liquid crystal compositions in which one type of chiral dopant is added as part or all of the chiral dopant are suitable. Also, by adding a small amount to nematic liquid crystal, TN
It can be used as a liquid crystal to prevent so-called reverse domains, or as an STN liquid crystal. The present invention also provides a method for producing a novel optically activated product having a cyano group represented by the above general formula (I). That is, an aldehyde represented by the following general formula (III) (wherein Rl represents an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkoxyl group, or an alkali group,
x2. y, 3 represents H, F or CN, but at least 1
The one is H<, Z+. Zz is independently COO.
OCO , CToO , OCHz or a single bond, m represents O or 1) is reacted with trimethylsilyl cyanide in the presence of a Lewis acid and an optically active diol to produce an optically active cyanandrine derivative represented by the following general formula (IV). shall be.

CN (having the same meaning, C" represents an asymmetric carbon atom with (I?) or (S) configuration) As the Lewis acid, titanium (TV) type is preferred, especially dichlorodialkoxytitanium or tetraalkoxy titanium Ethane is preferred. (Narasaka et al., Chem. Lett.,
1987. 2073 and Published Unexamined Publication No. 1983. 150. 2
No. 56). Optically active diol and 5: optically active 4.
Particularly preferred is 5-bis(diphenyl and do-Coxymethyl)-2-methyl-2-phenyl-1,3-dioxolane or tartaric acid ester.

Further, this reaction is preferably carried out in the presence of a dehydration condensation agent, particularly preferably carried out in the presence of molecular sieves.

As the solvent, ordinary hydrocarbon-based, chlorine-based, and alcohol-based solvents can be used, but toluene is particularly preferred.

Obtaining the compound of general formula (I) by reacting the cyanohydrin derivative represented by general formula (IV) with the carboxylic acid of general formula (V) represented by R''-COOII in the presence of a condensing agent such as DCC. I can do it.

R2 shown in the above general formula (V) has 1 to 15 carbon atoms.
any one or 2 to 3 non-adjacent alkyl groups of
CHZ can be replaced with 101, and any 1 CHHz can be replaced with 101.
~3 CH, are each independently, and when an asymmetric carbon is generated by substitution, the absolute configuration of the asymmetric carbon is (R).
(S) or a mixture thereof.
represents an asymmetric carbon atom with R) or (S) configuration.

The optically active compound having a cyano group represented by the general formula (I) of the present invention is obtained as described above, and individual specific compounds belonging thereto and the above general formula (III), (I
Specific intermediates belonging to V) etc. shall be confirmed by means of phase transition temperature such as melting point, elemental analysis, infrared absorption spectrum (rR), nuclear magnetic resonance spectrum (NMR), mass spectrum (MS). I can do it.

Examples of the compounds represented by the general formula (I) thus obtained are listed in Table 1. In the table, Cr is a crystalline phase, l is an isotropic liquid phase, SA is a smectic A phase, Scth is a chiral smectic C phase, and the numbers in parentheses indicate that the phase is monotropic pink. ☆ indicates that the presence of the phase can be confirmed under rapid cooling, but the transition temperature cannot be measured due to crystallization. For compounds with multiple asymmetric centers in the vicinity, optical purity is determined by NMR measurement value (diastereomeric excess)
For others (#), the intermediate cyanohydrin derivative is (R)-2-methoxy-2-phenyl-3
．． 3.3-} The value determined by NMR measurement of the ester compound obtained by reacting with fluoropropanoyl chloride is indicated by ee or de. If recrystallization is performed later, the optical purity will be even higher.

(Margins below this page) Although some of the compounds of the general formula (.1) of the present invention exhibit liquid crystal phases including the Sc" phase even when used alone, the two-ring type has poor liquid crystallinity, and the three-ring type has poor liquid crystallinity. Due to its high melting point, it is not very suitable for use alone.

In particular, when used as a ferroelectric liquid crystal display element, Sc" can be added as part or all of a chiral dopant to a Sc liquid crystal composition with low viscosity.
It is effective to use it as a liquid crystal display.

The above general formula (2) having an optically active group of the above general formula (II)
Examples of the Sc compound to be used as the Sc compound for doping the compound of I) include phenylbenzoate compounds represented by the following general formula (A) and pyrimidine compounds represented by the general formula (B). be able to.

(wherein R'' and Rh are linear or branched alkyl groups,
It represents an alkoxyl group, an alkoxycarponyl group, an alkanoyloxy group, or an alkoxycarponyloxy group, and may be the same or different.

(In the formula, R''ah is the same as the above general 2A.) In addition, compounds represented by the general formula (C), including the general formulas (A) and (B), can also be used for the same purpose.

(In the formula, R” R1 is the general formula A and . are the same, eagle, I, They may be the same or different.

What about z2? COO-, -0CO-, -CH20-, -OC
Rz-, -CH2CII1, 1CmiC-, represents a single bond. ) Also, for the purpose of expanding the temperature range of the Sc phase to a high temperature range,
A tricyclic compound represented by general formula (D) can be used.

(In the formula, R'' and R' are the same as or different from the general formula A, and Z'' and Z' are 2 of the general formula (C)
1, and may be the same or different. ) It is effective to mix these compounds and use them as a Sc liquid crystal composition, but it is sufficient that the composition exhibits an Sc phase, and it is not necessary for each individual compound to exhibit an Sc phase.

The general formula (I) of the present invention is added to the Sc liquid crystal composition thus obtained.
) 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. The liquid crystal assembly thus obtained can be used as a liquid crystal display cell by sealing it as a thin film with a thickness of about 1 to 20 μm between two transparent glass electrodes that have been subjected to alignment treatment.

In order to obtain good contrast, uniformly oriented monodomain cells are required. Many methods have already been tried for this purpose, but in general, as a liquid crystal material, Sc A liquid crystal that undergoes a phase transition to a ''' phase or an S, phase to an Sc''' phase,
Furthermore, it is known that the N'' phase and the Sc'' phase, especially those with a long thread pitch in the N'' phase, exhibit good alignment properties.

In order to increase the pinch of the thread, it is sufficient to mix appropriate amounts of chiral compounds whose oscillation directions are opposite to each other and use them as chiral dopants, but in this case, the spontaneous polarization
Care must be taken not to cancel each other out. The present compound represented by the above general formula (I) has at least one asymmetric carbon atom (C°), but the spontaneous polarization and the direction of the helical pitch induced by the compound (I) are C°. When the absolute configuration of is (R), e is on the left, and when (s), e is on the right. (The direction of spontaneous polarization is similar to that of P-decyloxybenzylideneaminocinnamic acid (S)-2-methylbutyl ester (DOBA), which is a well-known ferroelectric liquid crystal.
MBC ) is defined as e) Therefore, by combining with a known optically active compound whose induced spontaneous polarization and helical pitch are on the right in Φ or on the left in e, it is possible to induce spontaneous polarization. It is possible to increase the helical pitch without canceling each other out.

Examples of such a compound include, for example, a compound having an optically active group, -[1-t;-L;li-υ1K]. In compounds having only optically active groups whose induced spontaneous polarization is sufficiently small, such as CH, -COO CHzCH CzHs, the spontaneous polarization caused by these is much smaller than that of the compound of the above general formula (I), so the direction of the helical pitch It is also possible to mix them, taking into account the difference.

In addition to (c0), the present compound of the above general formula (I) also includes R
There are also compounds containing other asymmetric carbon atoms in R2 and R2. The presence of these asymmetric carbons in Rl and Rffi has the effect of further increasing the spontaneous polarization, or lengthening or conversely shortening the helical pitch, depending on its absolute configuration.

For example, in the compound of Example 9 (compound in Table INα9), when 5 to 10% is added to the Sc host liquid crystal described later, the helical pitch in the N'' phase is very long (more than 30 am), and the pitch is It is possible to obtain a Sc'' set exhibiting good distribution properties without any adjustment.

In addition, in the compound of Example 4 (compound in Table INα4) having an optically active group as R', 5
25°C (Tc-T
= 3 7@, tilt angle 23.7"), the spontaneous polarization value is 8.2 nC/cut, and that of the compound of Example 2 (compound of Table INα2) in which Rl is a straight-chain alkyl is 5. 6 nC/c{ (Tc-T = 30°
, a tilt angle of 20.1°), it can be seen that the tilt angle is extremely large.

Now, the greatest feature of the compound of general formula (I) above is that it can exhibit extremely large spontaneous polarization even when added in small amounts as a chiral dopant.

As shown in the Examples below, the above general formula (I) of the present invention
The spontaneous polarization of the Sc" compound obtained by adding 5% of the compound to the parent liquid crystal is 3.5 to 9.
nC/cd. It can be seen that this is a very large value when compared with that of DOBA MBC mentioned above, which is 2 to 3 nC/cTi even when used alone.

〔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.

C, the structure of the compound is determined by nuclear magnetic resonance spectrum (NMR)
, and was confirmed by infrared absorption spectrum (Il+) 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). (KBr) in IR indicates the tablet shape, and (neat) indicates measurement using a liquid film. N
In MR, (CDC l s) and (ccL) refer to the solvent, and S refers to l! ! line, d is double line, t is triple line, quint
et means quartet, sext means sextet, octe
t represents an octet, dt represents a double triplet, J represents a coupling constant, the high in MS represents a parent peak, and the number in parentheses represents the relative intensity of that peak. Furthermore, temperature is expressed in degrees Celsius. All percentages in the composition represent weight percentages.

Example 1 Synthesis of 4-((R)monocyano(pentanoyloxy)methyl)phenyl 4-decyloxybenzoate MS4A (4R, 5R)-4.5- at room temperature under argon atmosphere
Bis(diphenylhydroxymethyl)-2-methyl 72
-Phenyl-1,3-dioxolane Ig (I. 8 9
a+mof) toluene 20mj! Add 0.0% of dichlorodiisopropoxytitanium to the solution. 5 M toluene solution 3.3 ml (I.65 imol), and molecular sieves 4A (600 mesh)
1.8 g was added and stirred for 1 hour. 4-formylphenyl 4-decyloxybenzoate 299 ■ (0.78 o
After adding 10IIIl of toluene solution of 1), cool to -50°C and add 0.81ml of trimethylsilyl cyanide.
(6 mmof) was added and stirred for 27 hours. A pH 7 buffer was added to the reaction mixture, the temperature was returned to room temperature, the precipitate was filtered through Celite, extracted with ether, and separated by column chromatography (Wakogel C-200, hexane/ethyl acetate = 8/1). 4-decyloxybenzoic acid 4
- {(I?)monocyanohydroxymethyl}phenyl 282cm was obtained as a crude product (crude yield 88%, 91%ee). 93cm of this crude product was mixed with 2.5+a of dichloromethane.
0.15 mf of pentanoyl chloride at room temperature.
, pyridine 0.2mj! was added and stirred for 30 minutes. After water treatment and ether extraction, purification was performed by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1).
-decyloxybenzoic acid 4-{ (R) monocyano (
pentanoyloki)methyl}phenyl 94■ (yield 87
%).

Melting point: 63°C [αko 8.9” (c= 0.9
4,CHC13”)IR (KBr) 2920, 2
850. 1755 (C=O). 1730 (C=
0), 1605. 1510, 1470, 1320
, 1260, 1205. 1160,1090.
1060, 1005. 960, 870, 850
, 760, 690,650C heavy-1 II NMR (CDCf3) δ0.88 (t,
J = 6.5 Hz, 38), 0.93 (t, J
=6.5Hz. 38). 1.1 ~ 2.0 (m
．． 20 B). 2.43 (t, J=7.2 Hz
, 2 H), 4.05 (t+ J=6.5 Hz
．． 2H). 6.47 (s. L H). 7.0
(d, J=8.5 H2.2 H), 7.32
(d. J=8.5 Hz. 2 H). 7.0 (
d, J=8.5 Hz. 2 H), 7.32 (d
, J=8.5 Hz. 2 H), 7.6 (d,
J=8.5Hz. 2 H), 8.13 (d,
J=8.5 Hz, 2 H) MS m/z:
494 (M” + 1.0.04), 261
(I00), elemental analysis: C,. Calculated value as H,,No,: C, 72.99. H,? ．． 96
．． N, 2.84% Actual value: C, 72.76;
H, 8.16. N, 2.79% Example 2 Synthesis of 4-(4-octylphenyl)benzoic acid 4-{(R)monocyano(pentanoyloxy)methyl}phenyl (4R,5R)- at room temperature under argon atmosphere 4.5
-bis(diphenylhydroxymethyl)-2-phenyl-1,3-dioxolane 1 8 8 mg (0.3
6 mmoj! ) to 3 ml of toluene solution, add 0.0 ml of dichlorodiisoproboxytitanium. 5 4 M} toluene solution 0.55 ml (0.3 mmoj!), and molecular sieves 3A (600 mesh)
400 mg was added and stirred for 1 hour. 4-(4-
octylphenyl)benzoate 4-phoryl phenyl 60
■(0.15 mmof) of toluene 2III
After adding 0.1 solution of trimethylsilylcyamide, it was cooled to -50°C. 1 rsfl (0.8 mtao
1) was added and stirred for 8 hours. This reaction mixture has a pH of
7 was added, the temperature was returned to room temperature, the precipitate was filtered through Celite, and after extraction with ether, column chromatography (Wakogel C-200, hexane/ethyl acetate = 8/1
) and 4-(4-octylphenyl)benzoic 64
- ((R)monocyanohydroxymethyl}phenyl 52 µm was obtained as a crude product (crude yield 81%, 89% ee). 45 µm of this crude product was dissolved in 3 ml of dichloromethane, and 0.5 µm of pentanoyl chloride was dissolved at room temperature. 1IIll and 0.2 ml of pyridine were added and stirred for 30 minutes. After water treatment and ether extraction, purification by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) gave 4-(4-
octylphenyl) benzoate 4-((I?)monocyano(pentanoyloxy)methyl)phenyl49■
(Yield 9l%) was obtained. Melting point 67℃ [αko ”-9.9@ (c= 1.0 5
．． C! ICL)IR (KBr) 2930. 176
0 (C=O), 1730 (C=0). 1605
, 1505, 1470, 1400, 1265.
1205. 1155, 1105.10?5. 10
10. 960, 880, 820. 760C11
1-' heavy H NMR (CDCl s) 6
0.89 (t, J=7.5 Hz, 3
H), 0.93 (t, J=7.3 Hz, 3 H
), 1.2 to 1.45 (brm, 12H). 1
．． 6 to 1.72 (a, 4H). 2.37~2
．． 50 (m, 2H), 2.67 (t, J=7.
6 Hz, 2 H), 6.47 (s, I H
), 7.30 (d, J=8.3 Hz. 2 N)
, 7.34 (d, J=8.6 Hz, 2 H).
7.58 (d, J=8.3 1'lz.2 H),
7.60 (d, J=8.6 Hz, 2H)
, 7.73 (d, J=8.6 Hz, 2 H
), 8.24 (d, J=8.6 Hz. 2 }1
)MS m/z: 525 (M”+
0.5). 293 (I00) Elemental analysis'
Calculated value as CziHzJO: C, 77.
68; H, 7.48; N, 2.68% Actual value: C, ? 7.39; H, 7.66; N,
2.63% Example 3 4-[4-((s)-2-methylbutoxy)phenylcobenzoic acid 4-{(R) monocyano(pentanoyloxy)methyl}phenyl combination MS4A n with Example 1 Under similar conditions, 4-decyloxybenzoic acid 4
-4-[4~((s)-2 instead of formylphenyl)
Using 4-formylphenyl -methylptoxy}phenylnibenzoate, 4-14-((s)-2-methylbutoxy}phenyl]benzoic acid 14-{(R)monocyanohydroxymethyl}phenyl 159■ Yield 99
%, 92% de). Dissolve 153cm of this crude product in 5ml of methane, add 0.2ml of pentanoic O+J, and 0.5ml of pyridine at room temperature. apart,
Stirred for 30 minutes. After water treatment and ether extraction, thin layer chromatography (silica gel, hexane/ethyl acetate = 4
/l) to produce 4-[4-((s)-2
-Methylptoxy}phenyl]benzoic acid 4-((R)monocyano(pentanoyloxy)methyl}phenyl 128
(2) (yield 70%) was obtained. This was further purified by recrystallization (hexane/ether = 3/1) to obtain 4 [4
((s)-2-methylbutoxy}phenylcobenzoic acid 4-((R)monocyano(pentanoyloxy)
90 μm of methyl}phenyl (yield: 49%) was obtained.

? Point 135°C C 1 3 5 (Sc??) (Sa
78) 1 [α] o ” .5.9” (c ■
1.0 1, CHCfs)IR (neat)298
0. 1755 (C=O). 1740 (C=
0), 1605, 1510, 1470, 13
00, 1270. 1190. 11?0,
1150, 1070, 1010, 880,
830, 770, 695cm-''H NM
R (CDCj2 3) δ 0.93 (t,
J=7.4 Hz, 3 H), 0.97 (t,
J=7.5 11z, 3 El), 1.04 (d
, J=6.7 Hz, 3 N). 1.04 (
d, J=6.7 Hz. 3 }! ). 1.
24～1.34++112H)+1.37(
sextet, J=7.6 Hz. 2 H)+
1.55-1.74 (m, 2H). 1.9
0 (octet. J-6.7 Hz. 1 1{
), 2.37-2.51 (m. 2 H). 3.8
0 (dd, J=9.0, 6.6Hz+L H
). 2.06 (dd, J=9.0, 6.
6 Hz, IH). 6.47 (s, I
H), 7.01 (d, J=8.8 Hz, 2
H). 7.34 (d, J=8.6 Hz.2 H
), 7.59 (d, J=8.8 Hz, 2 H)
, 7.60 (d. J=8.6 Hz, 2 B
), 7.70 (d, J=8.5 Hz. 2 H
). 8.22 (d, J=8.5 Hz, 2
H) MS m/z: 499 (M”
, < 1), 267 (I00) Elemental analysis: Calculated value as C31833NOS: C,
? 4.53. H, 6.66. N, 2.80
% Actual value: C, ? 4.29 i H, 6.81
．． N, 2.73% Example 4 4- [4- ((R)-1-methylhebutyloxy}
phenyl]benzoic acid 4-{(R)monocyano(pentanoyloxy)methyl}phenyl H S4A CN Under the same conditions as in Example 1, 4-decyloxybenzoic acid 4
- instead of formylphenyl, 4- [4-( (R
)-1-methylheptyloxy}phenyl]benzoic acid 4
Using -formylphenyl, 4- [4- ((R)
-1-Methylheptyloxy}phenyl]benzoic acid 4-
{(R}-cyanohydroxymethyl}phenyl crude product (
Crude yield 88%. 90% de). This crude product 8
Dissolve 7■ in 3 ml of dichloromethane and add 0.1 mj of pentanoyl chloride at room temperature. , Pyridine 0.2 wf! was added and stirred for 30 minutes. After water treatment and ether extraction, purification by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) yielded 4-[4- {(R)-1-
Methylheptyloxy}phenyl]benzoic acid 4-{(R
) monocyano(pentanoyloxy)methyl}phenyl8
4a+g (yield 82%) was obtained. Furthermore, this was recrystallized (
Purification was performed using hexane/ether (3/1) to obtain a pure product of the same compound, 46 ml (yield: 44%). Melting point 63°C [α]D! o 9-1゜(c = 1.01, C
HCI ls) IR(κB, ”) 2950
．． 1770 (C.O.). 1735 (C.O.)
．． 1605.1510. 1470. 138
0. 1300. 1265. 1220,
1200.1280, 1145. 1105.
1070. 1030. 1015, 960
,870, 830, 810, 770,
700, 505cm-''H NMR (CDCl
! )60.89(t, .r・7.0 Hz,
3H). 0.93 (t. J-7.3 Hz .3
}1). 1.34(d, J=6.1 11z
,3 1{). 1.25 ~ 1.83 (■, 14
II). 2.38 ~ 2.50 (m. 2H
). 4.42 (sextet, J=6.1 Hz
tL H). 6.47(s.IH)+7.0
0 (d, J=8.8 Hz, 2 H), 7.3
3 (d, J.8.7 Hz .2 H). 7.
59 (d, J・8.8 Hz .2 H). 7
．． 60 (d. J. 8.7 Hz. 2 B).
7.70 (d, J=8.6 Hz .2 1
'l). 8.22 (d, JJ.6 H2.2 H)
MS s/z: 54HM". 2). 19
7 (97). 57 (75), 43 (I00) 41 (82
). 29 (88) Elemental analysis: Calculated value as CsJsJOs: C. 75.39 iH. 7.26
．． N. 2.59% actual value: C. 75.22
．． H. 7.41; N. 2.57% Example 5 4-(4-octylphenyl)benzoic acid 4-[(R)monocyano((S)-2-methylbutanoyloxy}methyl]phenyl) Same as Example 2. The crude product of 4-((R)monocyanohydroxymethyl)phenyl 4-(4-octylphenyl)benzoate 106+ag (89%ee
) was dissolved in 3 ml of dichloromethane and heated to room temperature (S)-
2-methylbutanoyl chloride 0.1■21 pyridine 0
．． 3mf was added and stirred for 3 hours. After water treatment and ether extraction, it was purified by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) to obtain 4-(4-octylphenyl)benzoic acid 4-[(R) monothia/{(S
)-2-methylbutanoyloxy}methyl]phenyl 5
2■ (yield 43%, 80% de) was obtained. ? Point 75°C [αko o” 4.3° (c = 0.99,
CHC1 x) IR (KB, ) 2950.
1750 (C.0). 1735 (C・0),
1610.1510. 1460. 1270.
1215, 1170. 1120, 108
0,1015. 875, 820, 765,
690 cm-''H NMR (CDC 1 3)
δ0.89 (t, J=7.5 FI2,6 H)
, 1.22 (d, J・7.0 Hz, 3 H),
1.23 to 1.80 (s+. 14 H). 2.5
0(sextet, J=6.7 Hz, IH
). 2.67 (t. J=7.9 Hz
．． 2 H). 6.48 (s.I.H.).
7.30 (d. J=8.3 Hz, 2
H), 7.34 (d, J・8.I B
Z. 2 H) 7.58 (d, J ■ 8.3 H
z, 2 11), 7.60 (d, J■8.
7 Hz2 H), 7.73 (d, J・8.6
fiz l2 H). 8.24(d, 8.
7Hz. 2 H). MS m/z: 525 (M″.0.5).
293 (I00) Elemental analysis: Calculated value as Cs4H3JO4: C, ? ? ．． 68; H. 7.4
8; N. 2.66% actual value: C, 77.5
0. H. 7.65. N. 2.60% Example 6 4-decyloxybenzoic M4- [(R)monocyano(
(S) -2-Methylptanoyloxy}methyl]phenyl synthesis n Crude product of 4-decyloxybenzoic acid 4-{(R)monocyanohydroxymethyl}phenyl synthesized in the same manner as in Example 1 110■ Polyphosphoric acid ethyl ester (PPE)
-Chloroform solution 1. 5 tar! (Bioc
hem. Biophys. Acta. JLL.
1 (I964). ) and at room temperature (S)-2-
50 μl of methylbutanoic acid was added and stirred for 1 hour. Add saturated aqueous sodium bicarbonate solution, extract with ether, and purify with thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) to obtain 4-decyloxybenzoic acid 44(R) monocyano ((S)-2 -Methylbutanoyloxy}methylcophenyl 115■ (yield 87%) was obtained.Furthermore, the same compound 92■ (yield 69%, >95% de) was obtained by recrystallization from hexane. Melting point 39°C Eff at O1.5° (c = 1.07, CHC1
s>IR(KB, ”) 2920.1760(
C. O). 1730 (C.O), 1605.151
0. 1470, 1310. 1250, 1205
, 1165. 1130.10?0, 1010,
945, 875, 840, 810,
760, 685, 655. 535 cta-
'In NMR (CDCj!3) 6 0.88 (t.
J=7.5 12. 3H), 0.89(t,
J. 7.0Hz. 3H). 1.21(d, J
．． 6.9 }1z , 3 B), l. 21-1-58 (
s+ 15 H), 1.65-1.76 (m.I
H). 1.82 (quintet, J=6.6 Hz
l2 1f) + 2.49 (sextet, J = 6.9
Hz + I H). 4.05 (t, J=6.6
HZ, 2 H). 6.47 (s, IH).
6.97 (d. JP9.0 Hz, 2H), 7
．． 30 (d, J・8.6 H2.2 H). 7.
58(a, J.8.6 H.2 B). 8.13 (
d, J・9.0 Hz. 2H)MS ta/z
: 493 (M'< 1). 26H83). 1
2H100) Elemental analysis: C,. Calculated value as HswNOs: C, ? 2.99. }l, ? ．． 96
．． N, 2.84% Actual value: C. 73.11
;■． 8.03; N. 2.85% Example 7 4-decyloxybenzoic acid 4-[(S)monocyano(
S) Synthesis of -2-methylbutanoyloxy)methyl]phenyl? IS4 A n Under conditions similar to Example 1, (4R, 5R)-4.5
-bis(diphenylhydroxymethyl)-2-methyl-
Instead of 2-phenyl-1,3-dioxolane, (4
5,5S)-4.5-bis(diphenylhydroxymethyl)-2-methyl-2-phenyl-1,3-dioxolane was used to prepare 4-decyloxybenzoic acid (41(S)monocyanohydroxymethyl) phenyl crude ( Crude yield 89%
, 90%ee). P of this crude product 164
Dissolve PE in 1 ml of chloroform solution and stir (S
) 1-2-methylbutanoic acid 0.1a+j! was added and stirred for 1 hour. Add saturated aqueous sodium bicarbonate solution, extract with ether, and purify with thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1) to obtain 4-decyloxybenzoic acid 4-[(S) monocyano{(S) -2-Methylbutanoyloxy}methyl]phenyl 181cm (yield 92%) was obtained. This was recrystallized from hexane to obtain the same compound 129 (yield 65%.>95% de). Melting point 38°C [α]1°+12.2 @(c=0.97, CHCj
! s) IR (KB, ) 2920. 1750 (
C. 0), 1730 (C.0). 1605,151
0. 1465, 1320. 1260, 1205
, 1165. 1115.1060. 1020,
995, 950. 870, 840,
760,650 cm Direct 'H NMR (CDCN x) 60.89 (t. J
・7.0 Hz, 3 H). 0.94(t, J
=7.5Hz. 3H). 1.18(d,
J=7.0Hz. 3H). 1.23 ~ 1.8
2 (e+. 15 H). 1.68 ~1.80
(m. I H). 1.82 (quintet,
J=6-6 Fk. 2 H>. 2.49 (sa
xtet. J・6.9 Hz, 2 H). 4.
04 (t. JJ.6 1h, 2 B). 6
．． 46 (s, L H), 6.97 (d, J=9
．． 0 Hz, 2 B), 7.30 (d, J=
8.6Hz. 2 H). 7.58 (d.
J. 8.6 1'lz+2 H). 8.13 (d.
J. 9.0 H2. 2 B) MS va/
z: 493 (M". 0.5).
261 (I00), 121 (44). Elemental analysis:
Calculated value as C311}139NOS: C.
72.99 ;H. 7.96; N. 2.84
% Actual value: C. 72.96; H. 8.10
;N. 2.83% Example 8 4-decyloxybenzoic acid 4-[(R)monocyano { (
S) -2-Ptoxypropanoyloxy}methyl]phenyl combination DMAP CN dicyclohexylcarbodiamide (DCC) 220mg
(S)-2-Butoxypropane in a 5 yal solution of dichloromethane! o. 4-decyloxybenzoic acid 4-((R
) monocyanohydroxymethyl}phenyl crude product 142
mg of dichloromethane 1/2 solution and 4-dimethinorea ξ
2.21 g of nobilidine (DMAP) was added and stirred for 30 minutes. After water treatment and ether extraction, purification was performed by thin layer chromatography (silica gel, hexane/ethyl acetate = 4/1), and 4-decyloxybenzoic acid 4-[(R)monocyano((S)-2-ptoxy) Bropanoyloxy)methyl]phenyl 168a+g (yield 90%) was obtained. Further, the same compound was recrystallized from hexane to yield 109 mg (yield 59
%, 〉95%de) was obtained. Melting point 48°C [α] o”-34.3 @(c-1.05.CHC
j! s) IR (KB, ) 2930. 1760
(C=0). 1740 (C=0). 1610.15
10. 1310. 1255. 1210, 115
0. 1080, 1020, 875, 840,
760 cm-''H NMR (CDCf3)
6 0.89(t, J 7.0 Hz,
3 B). 0.91 (t, J=7.4 Hz, 3
H). 1.40 (d, J-6.9 Hz .3
H). 1.22 ~ 1.62 (s. 18 H), 1
．． 82 (quintet, J-7.0Hz l2H
), 3.40 (dt. J=8.9.6.5 Hz
, IH). 3.55 (dt, J・8.9.6
．． 5 Hz. 1). 4.04 (t, J・6
．． 6Hz. 2 H) + 4.05 (quinte
t, J=6.9 Hz lI H ). 6.5H
s. L H), 6.97 (d, J-9.0 H
z, 2 H), 7.31 (d, J wealth 8.6
H2. 2H). 7.58 (d.J=8.6
1h. 2H), 8.13(d, J=9.0
Hz. 2 B) MS mHz: 537 (M
”, < 1) .261(I00)., 12
1 (63) Elemental analysis Calculated value as C3zHaxNOb: C, 71.48; H, 8.06.
N. 2.60% actual value: C. 71.63 ;H
, 8.15. N, 2.56% Example 9 4-decyloxybenzoic acid 4-[(S)monocyano( (
S) -2-Butoxypropanoyloxy)methyl]phenyl DMAP CN DCC 1 8 1 g of (S)-2-butoxypropanoic acid in 3 ml of dichloromethane solution with 0.1 mj of (S)-2-butoxypropanoic acid! Add
Furthermore, 152 g of a crude product of 4-{(S)monocyanohydroxymethyl}phenyl 4-decyloxybenzoate synthesized in the same manner as in Example 7 and 3 tal of dichloromethane were added.
The solution and 2.9 mg of DMAP were added and stirred for 30 minutes. After water treatment and ether extraction, thin layer chromatography? Purified with silica gel, hexane/ethyl acetate-4/1),
4-decyloxybenzoic acid 4-[(S)monocyano ((
180 mg (yield 90%) of S)-2-ptoxypanoyloxy)methyl]phenyl was obtained. Further, recrystallization from hexane yielded 95 mg of the same compound (yield 48%.〉95%).
de) was obtained. Melting point 45℃ [α] 1°-8.4° (c=1.oO, CHC l
s) IR (KB, )2930. 1770 (C=
0), 1730 (C.0). 1605.1510.
1470. 1260. 1215. 11?0.
1125. 1070.1010. 950, 8
45,760 cry-''H NMR (CDC
12 s) 60.89 (t. J・7.0 Hz
．． 3H). 0.91 (t, J=7.4 Hz .3
H), 1.46 (d, J depth 6.9 ax, 3u
), 1.22 to 1.62 (m, 18 H), 1.
82 (quintet. J-7.OHZ, 2 }1
). 3.39 (dt. J=8.9.6.5 Hz
．． I n ). 3.54 (dt. JJ.9 6.
5 Hz. IH). 4.04 (quin-te
t, J■6. QHz. IH). 4.05(
t. J.J. 6 Hz, 2 H). 6.51
(s. I H). 6.97 (d, J=9.0
Hz. 2 1 {). 7.31 (d, J・8
．． 7 82. 2H), 7.60(d,
J=8.7 Hz, 2 H). 8.13(d, J
-9. O H2.2 H) MS s/z: 537 (M”,
<1). 261 (I00).
12H93) Elemental analysis' Calculated value as CxzHaxNOh: C, 71.48; H, 8.06;
N, 2.60% actual value: C. 71.50;
H. 8.21: N. 2.59% Example 10 4-[4- ((S)-2-methylptoxy}phenyl]benzoic acid 4-((S)monocyano ((S)-2-
Synthesis of methylbutanoyloxy)methyl]phenyl MS4A CN PPE (4S, 55)-4.5 at room temperature under argon atmosphere
-bis(diphenylhydroxymethyl)-2-methyl-
2-phenyl-1,3-dioxolane 4 8 5mg
(0.9 2 mmol) in a solution of 1 OII in toluene,
0.0 of dichlorodiisopropoxy titanium. 5 M}Luene solution 1.5a+j! (0.75 mmol), and further Molecular Sheeps 4A (600a+esh
) 950+g was added and stirred for 1 hour. 4- [4
- {(S)-2-Methylbutoxy}phenyl]benzoic acid 4-honoretanolepheninole 15 6mg (0.
After adding 40 msol) of toluene 10a+f solution, it was cooled to -60°C and 0.3 msol of trimethylsilyl cyanide was added.
5mj! (2.6 mmol) was added and stirred for 59 hours. A pH 7 buffer was added to this reaction mixture, the temperature was returned to room temperature, the precipitate was filtered through Celite, extracted with ether, and separated by column chromatography (Wakogel C-200, hexane/ethyl acetate = 5/1). [4- (
(S)-2-methylbutoxy}phenyl]benzoic acid 4-
((S) monocyanohydroxymethyl}phenyl 143I
lg was obtained as a crude product (crude yield 86%, 88% de). Add 135 mg of this crude product to 2 ml of PPE-chloroform solution! (S)-2-methylbutanoic acid at room temperature. 1 ml was added and stirred for 1 hour. Add saturated aqueous sodium hydrogen carbonate solution, extract with ether, and purify with thin layer chromatography (silica gel, benzene) to obtain 4-
[4- ((S)-2-methylptoxy}phenyl]
124 Ill of benzoic acid p-[(S)monocyano ((S)-2-methylbutanoyloxy}methyl-1 phenyl) was obtained (yield 76%). This was recrystallized from hexane to give 108 mg of the same compound (yield 67%). %, 〉95% de). Melting point: 120°C [a] a”+19.5” (c=1.02, C
HCl s) IR (KB, ) 2980. 1
770 (C・O), 1735 (C・0). 1605
．． 1515. 1465. 1295. 1270,
1210. 1200. 1170.1110. 10
? 5, 1025. 1010, 1000, 95
5,825,765 ccg -''H NMR (CDCl s) δ0.95 (t, J
=7.5 }1z. 3H), 0.97(t, J
=7.5Hz. 3 II). 1.04(d, J
・6.7 Hz, 3 H), 1.18 (d, J=
7.0 Hz, 3 Fl). 1.24-1.3
6 (m. IH), 1.50 ~ 1.65 (m
．． 2H), 1.69-1.8Hm, LH)
, 1.87-1.95 (m, 1 }1), 2.
50 (sextet, J=6.9 Hz.
I H), 3.80 (dd, J=9.0, 6.6
Hz. IH), 3.89 (dd. J=9.
0. 6.0Hz. IB), 6.47 (s.
18). 7.01(d, JJ.8 1h,
2 H). 7.34 (d, J・8.7 Hz, 2
H). 7.59 (d. J curve 8.8 Hz, 2H
), 7.60 (d, J・8.7 Hz . 2 H
), 7.70 (d, J・8.6Hz, 2H)
．． 8.22 (d, J・8.6112.2H)
MS mHz: 499 (M”.0
．． 4). 267 (I0G), elemental analysis: CxrH
Calculated value as s3NOs: C. 74.53;
H. 6.66: N, 2.80% actual value: C
．． 74.26:H. 6.66 S N, 2.7
7% Example 11 4-[4- ((S)-1-methylbutyloxy}phenyl]benzoic acid 4-[(S)monocyano ((S)-
Synthesis of 2-methylbutanoyloxy}methyl]phenyl or [4-{(S)-2-methylbutoxy}phenyl]benzoate instead of 4-formyl phenyl under similar conditions as in Example 1 O 4-[4-[(S)-1-methylheptyloxy}phenyl]benzoic acid using 4-formylphenyl 4-[4-{(S)-1-methylheptyloxy}phenyl]benzoate 4-((S)monocyanohydroxymethyl}phenyl crude product (crude yield 94
%. 90% de). This crude product 156a+g
was dissolved in 3 ml of PPE-chloroform solution and heated to room temperature with 0.1+/! of (S)-2-methylbutanoic acid. was added and stirred for 2 hours. Add saturated aqueous sodium bicarbonate solution, extract with ether, and purify with thin layer chromatography (silica gel, hexane/ether = 5/1) to obtain 4-[4-
{(S)-1-methylheptyloxy}phenyl]benzoic acid 4-[(S)monocyano {(S)-2-methylptanoyloxy}methyl]phenyl 165 mg (yield 8
9%). This was recrystallized from hexane to obtain the same compound 1.
35 mg (yield 73%, >95% de) was obtained. Melting point 8
5゜C [α] D"+10.3" (c=0.99, CHC
f 3) IR (KB, ) 2950. 1763
(c=0), 1735(c・O), 1603,15
10. 1270, 1210, 1195. 117
0. 1130. 1070.1010. 830.
765 cra-''H NMR (CDCj!
3) δ0.89 (t, J・7.0 Hz .3
) I), 0.95 (t, J・7.5 1Lz .3
H), 1.18 (d, J・7.O f!2.3
1), 1.25-1.66 (i+.10H),
1.34 (d, J=6.1 Hz, 3 H)
．． 1.69 to 1.82 (m. 2 H). 2.5
0(sextat, JJ.9 Hz IH)+4.
42 (sextet. J=6.L L +I H
). 6.47 (s, IH). 6.99 (L,
J=18.8 Hz, 2 1{ ), 7.
34 (d, J・8.6 82, 2 H). 7
．． 59 (d, J・8.8 Hz. 2 II).
7.60 (d, J・8.6 nz, 2 H).
7.70 (d. J・8.6 Hz, 2 H)
8.23 (d, J・8.611!, 2
H) MS m/z: 541 (M”. 1.8
)． 309 (I00), 197 (81) Elemental content Fr: Calculated value as CsJsJOs: C.
75.39; H, ? ．． 26. N, 2.59
% Actual value: C, ? 5.40; H. 7.25
:N. 2.49% Example 12 4- [4- {(S)-1-methylhebutyloxy}
phenyl]benzoic acid 4-rts) monocyano{(S)-2
-butoxypropanoyloxy}methyl]phenyl OBu DMAP CN To a 3 ml solution of DCC150a+g in dichloromethane (
4- [4- (
A solution of 155 mg of crude product of (S)-1-methylheptyloxy}phenyl]benzoic acid 4-{(S)monocyanohydroxymethyl}phenyl in 5 mJ2 of dichloromethane and D
2 mg of MAP was added and stirred for 1 hour. After water treatment and ether extraction, purification by thin layer chromatography (silica gel, benzene/ethyl acetate = 20/l) was performed. -Tesyloxybenzoic M4- [(S)-C7/ ((S)-2
-butoxypropanoyloxy}methyl]phenyl 14
7a+g (yield 74%) was obtained. Further, 103 mg of the same compound was recrystallized from a 5/1 hexane/ether mixture (
A yield of 52%, >95% de) was obtained. Melting point 66℃ [α]. ″”-7.9° (c■1.OO, CHCfz
)IR(XB, )2940. 1780 (C.
0), 1725 (C.0). 1605, 1510,
1270, 1190, 1120. 10?5.
1015. 830,770 cm-' IH NMR (CDCj!x) 6 0.89 (t.
J. 7. O H2. 3H). 0.92(t, J
．． 7.4Hz. 3H). 1.34 (d, J wealth 6.1 12.3 B), 1.46 (d. JJ.9
HZ, 3 H). 1.26-1.65 (m. 13
H). 1.72-1.83 (m.IH), 3.
39 (dt. J・8.9.6.5Hz.2
H). 3.55 (dt, J・8.9. 6.5
82, I H), 4.04 (q. J=6.9
Hz. IH). 4.42 (sextet, J
=6.1 Hz, IH). 6.52(s,
IH). 6.99 (d, J=8.8 Hz,
2 H). 7.35 (d, J・8.7 82.
2 R). 7.59 (d, J.8.8 82
．． 2 n). 7.62 (d, J・8.7H1.
2 B), 7.70 (d. J・8.6 N2
．． 2 B). 8.22 (d, J・8.6 H2
．． 2H)MS mHz: 585 (
M”.1.4).309(I00)
．． 197 (85) Elemental Analysis Calculated value as CsJaJOa: C, 73.82; H. 7.40.
N. 2.39% actual value: C. 73.89 i
H. 7.50. N. 2.30% Example 13 (S)-2-Methylbutanoic acid (S)monocyano[4- (
Synthesis of 4-(4-pentylphenyl)phenyl}phenyl]methyl MS4A n Under conditions similar to Example 10, 4-[ 4-[(S)
-2-methylbutoxy}phenyl1benzoate Instead of 4-formylphenyl, 4-(4-(4-pentylphenyl)phenol}benzaanoledehyde 290+s
(S)-2-hydroxy-2-[4-
(4-(4-pentylphenyl)phenyl}phenyl]
Obtained as crude acetonitrile (crude yield 57%, 93% de).

This crude product 170+ag@PPE-Chloroform solution 2
Dissolve (S)-2-methylbutanoic acid in lI1 at room temperature.
．． 1mj! was added and stirred for 2 hours. Add saturated aqueous sodium bicarbonate solution, extract with ether, and purify with thin layer chromatography (silica gel, benzene) to obtain (S
)-2-methylbutanoic acid (S) monocyano[4- {4-
(4-pentylphenyl)phenyl}phenyl]methyl 139+og (yield 66%) was obtained. Add this to hexane/
Reconsolidation from ether = 5/1 mixture? The same compound 86mg
(yield 4l%, >95%de) was obtained. Melting point 124°c C124 (Sa??) I [α]
ot0+23.1@(c-0.99.CHCls)I
R(KB, ) 2930. 1760 (C-0)
．． 1495 (C tonnage 0). 1460.11?5. 1
125. 1090. 1000. 950, 8
05. 5000 carcasses 1'H NMR (CDCl3) δ0.92 (t.J
=7.1 Hz, 3 H). 0.95(t, J■
T. 4 Hz, 3 H). 1.19 (d. J■1
．． OHz. 3 H), 1.3 to 1.42 (a+.
4 H). 1.50~1.82 (s. 4H),
2.51 (sextet, J-6.8.Hz.
IH). 2.66 (t, J=7.9 Hz.
LH). 6.49 (s.IH), 7.2
8 (d, J=8.2 [2.2 H). 7.56
(d, J=8.2 II z .2 n). 7.6
0(d, J=8.3 Hz.2 n). 7.6
6 (d, J=8.7Hz.2H). 7.69
(d, J・8.7 h, 2 n). 7.71
(d. J・8.3 82.2 H) MS cm/
z: 439 (M”, 100), 338
(45). Elemental analysis: C. Calculated value as H33NOf: C, 81.97; 7.57
．． N, 3. ! 9% actual value: C, 81.86
;H. 7.61; N, 3.10% Example 14 4-C4- (<R>-1-methylhebutyloxy}
phenyl]benzoic acid 4-[(R)monocyano{(25.3
5) Synthesis of -2-chloro-3-methylpentanoyloxy}methyl]phenyl CM! ,1 CMAP CN DCC in a solution of 175 mg in 3 tsl dichloromethane (
2S. 3S)-2-chloro-3-methylpentanoic acid 13
0■ was added, and 4-
[4-((R)-1-methylheptyloxy}phenyl]benzoic acid 4-((R)monocyanohydroxymethyl}
155 mg of phenyl crude dichloromethane l ra1
The solution and 2.5 mg of DMAP were added and stirred for 1 hour. After water treatment and ether extraction, purification by thin layer chromatography (silica gel, hexane/ethyl acetate = 5/1),
4-[4-((R)-1-methylhebutynoleoxy)phenyl]benzoic acid 4-[(R)monocyano((2S
, 3S)-2-chloro3-methylpentanoyloxy}methyl]phenyl (185 mg (yield 92%)) was obtained. Further, it was recrystallized from ethanol to obtain the same compound 79ieg (yield 39%, >94% de). Melting point 82°C [α] 11”-6.3° (c=1.08.CHC
i 3) IR (KB, ') 2950. 17
60 (+, O), 1735 (C=O), 1610.
1510. 1280. 1210. 1175. 1
140. 10?5, 830.770 cta-''H NMR (CDC f3) δ0.88 (t, J
=7.5Hz. 3 H), 0.89 (t. J=
7.0 Hz, 3 1'l). 1.00 (d.J
=6.8 1{Z,3}1),1.34(d, J
・6.1 Hz. 3 H), 1.24 to 1.50 (excitation, 9}1), 1.52 to 1.65 (+n, 2 H)
．． 1.52-1.65 (m, 2H) 1.72-1
．． 83 (m, L H), 2.03-2.14 (m
．． IH). 4.25 (d, J=7.0 Hz,
IH), 4.42 (sextat, 6.1
Hz. LH). 6.50 (S.L.H.)
, 6.99 (d, J・8.8 tt. . 2
B). 7.36 (d, J=8.6 12, 2
H) 7.59 (d. J・8.8 Hz. 2
H). 7.62 (d, J・8.6Hz.2
It). 7.70 (d, J.8.6 112.
2 1'l), 8.22(d, JJ.6 Hz
, 2H) MS ta/z: 589 (M
”.1.0), 309(I00).197
(92) Elemental analysis: C3, ■4. Calculated value as C I NOs: C, 71.23. H, 6.83
; N, 2.37CL6.01% Actual value: C, ? 1.33; 11, 6.90
;N. 2.44Cl. 5.80% Example 15 4- [4- ((S)-1-methylheptyloxy}
phenyl]benzoic acid 4-[(S)monocyano ((2S,
3S)-2-chloro-3-methylpentanoyloxy)
Methyl] phenyl combination or CM and 2 CMAP CN DCC 170 mg of dichloromethane 3llj! into the solution (
25.3S)-2-chloro-3-methylpentanoic acid 13
0■ was added and further synthesized in the same manner as in Example 1l.
- [4- {(s)-1-methylheptyloxy}phenyl 1benzoate 4-((S)monocyanohydroxymethyl}phenyl crude product 152 ml in dichloromethane)
The solution and DMAP2.3+ag were added and stirred for 1 hour.
After water treatment and ether extraction, purification by thin layer chromatography (silica gel, hexane/ethyl acetate-5/l) yielded 4-[4-{(S)-1-methylheptyloxy}phenyl]benzoic acid 4- [(S) One cyano( (2S
, 3S) -193 mg (yield 98%) of 2-chloro3-methylpentanoyloxy}methyl]phenyl was obtained. Further, it was recrystallized with ethanol to obtain 60 sg of the same compound (yield 30%, >95% de). Melting point 67°C [α] a” + 3.3° (C・1.03.CHCigo) IR (KB, ) 2930. 1770 (C=
0), 1730 (C・0), 1600, 1510,
1270, 1205, 1170. 10?0,
990, 820.760 cta-''H NMR (CDCI! 3) 60.89 (t.J
=7.0Hz. 3 B). 0.94(t, J=
7.4Hz. 3■), 1.03(d, J=6.
8 Hz, 3 H), 1.34 (d, J6.I
HZ,3}1). 1.25-1.52 (m, 9
H), 1.55 to 1.72 (+s, 2H). 1
．． 73-1.84 (m.IH). 2.06-2.1
8 (m. 1 }1). 4.24 (d, J・6.9
Hz, l■). 4.42 (Sextet. 6
．． 1Hz. l B). 6.49 (s, 1u).
6.99 (a. J=8.8 HZ. 2 a).
7.36 (a, JJ.6 Hz. 2 H),
7.59 (d. JJ.8 Its.2 H). 7
．． 62 (d, J.8.6 H., 2 II),
7.70 (d, J・8.5Hz.2H),
8.22 (d, J=s.s Hz .2 H) MS
ta/z: 589 (M". 1.4)
, 309 (I00). 197(83) Elemental analysis:
Calculated value as C3sHsoC 12 NOs: C,
? 1.23: H, 6.83. N, 2.3
7(t', 6.01% Actual value: c, 7t.l6; a. 6.91;
N. 2.67C' = 5.83% Examples 16-18 In the same manner as in Examples 1-15, each compound in Table INO16-18 was obtained.

Its physical properties are summarized in Table 1. Example 1 (S)-4-{cyano(hexanoylsoxy)methyl}
Preparation of 4-octyloxyphenyl benzoate under argon atmosphere at room temperature (4R,5R)-4.5-bis(diphenyloxymethyl)-2-methyl-2-phenyl-L3-dioxolane 640 111 g (I.2 mm
8ml of tonoleen? To the solution, add 2 ml of a 0.5 M toluene solution of dichlorodiisoproboxytitanium (
I mmol), and further molecular sieves 4A (
600 mesh) was added and incubated for 1 hour. After adding a solution of 182 mg (0.51 vnol) of 4-formyldebenzoic acid 4-octinoleoxyfunilate in toluene 4I1, it was cooled to -60°C and 0.4 ml (3 mmol) of trimethylsilyl cyanide was added. ,
It was stirred for 16 days. Pll 7 buffer was added to this reaction mixture, the temperature was returned to room temperature, the precipitate was filtered through Celite, and after extraction with ether, column chromatography (Wako Gel C-
200. Separated with hexane/ethyl acetate = 8/1),
(S)-4-(cyanohydroxymethyl)benzoic acid 4-
57 mg of octyloxyphenyl was added to the crude product (crude yield 2
9%, 36%e6). This crude product 52
mg was dissolved in 2 ml of dichloromethane, 0.1 ml of hexanoyl chloride and 0.2 ml of bilicin were added at room temperature, and the mixture was incubated for 1 hour. After water treatment and ether extraction, it was purified by thin layer chromatography (silica gel, hexane/ethyl acetate, 4.,'1>) to obtain (s)-4-[cyano(hexanoyloxy)methyl benzoic acid]. 55 mgl of 4-octyloxy7enyl (yield: 83%) was obtained. Melting point 62-63℃ IR (KBr) 2950, 28aO, 1760 (
C=0). 1750 (C=0). 1610. ! 510,
1480, 1275, 1250. 1190, 1
180.11?0.1020.760 am-'1HN
MR (CDC x,) 60.89 (t.,
J=5.7Hz, 6H), 1.0~2.0(m
．． 18 Fl), 2.44 (t, J=7.4 Hz,
2 H), 3.96 (t., J=6.3 Hz, 2
H). 6.51 (s, I H), 6.92 (d, J=9
．． 3 }1z, 2 H). 7.12 (d. J=9.3
Hz. 2 11), 7.65 (d.J=8.4H
z. 2 1 {), 8.27 (d, J=8.4 Hz
．． 2H) Examples 20 to 24 (1M Preparation of liquid crystal composite bottom using compound of formula (I) and preparation of display element)
Body liquid crystal tone! ! ! ) A Sc matrix liquid crystal consisting of the following combinations was prepared. Hereinafter, it will be referred to as parent liquid crystal CA).

28% by weight 20% by weight This base liquid crystal (A) has an SC phase at 68.5°C or less, 73
．． It exhibited an SA phase at temperatures below 5°C and an N phase at temperatures below 83.5°C, and its melting point was 13.0°C.

In addition, an SC matrix liquid crystal consisting of the following U precepts was prepared.

Hereinafter, it will be referred to as base liquid crystal (B).

12.5% 12.5% and 115% 20% 20.0% 20.0% 10.0% This base liquid crystal (B) has N phase and 9
The SA phase was shown at 0°C or below, and the Sc phase was shown at 87.5°C or below.

Example 20 (Preparation of Sc."Ml precept using compound (I) and creation of display element) Phase transition temperature of SCs composition consisting of 95% of parent liquid crystal (A) and 5% of compound @IJ of Table IN01 (The melting point was unclear.) ('C) This composition was heated to an isotropic liquid phase, and polyimide It was filled between 21 transparent electrodes that had been subjected to coating-rubbing orientation treatment, and then slowly cooled to room temperature to obtain an oriented Sc" phase thin film cell.

This cell has an electric field strength of 50 Hz with an electric field strength of 10 Vp-p/μ.
When we applied a square wave of 2 and measured the optical response, we found that 2
The response was 79 μs at 5°C and 62 μs at 30'C. The spontaneous polarization at 25°C is 5.6nC/d,
The tilt angle at that time was 21.5°.

When the proportion of the NOI compound was set to 7%, the response at 25°C was even faster at 54 μsec. The phase transition temperature of this composition is as follows.

(°C) Example 2l In Example 20, instead of the NOI compound, NO2
Table 2 shows the results obtained using the same compound.

(Margin below this page) Example 22 Table 3 shows the results of the same experiment using the NO5 compound.
Shown below.

(Margin below this page) Example 23 Similarly, No. 3, No. 4. NO6. NO7,
NO8. NO9. A NOIO compound was added to a host liquid crystal, and its phase transition temperature, chemical response, and spontaneous polarization were measured. (Both at 25°C) The results are shown in Table 4. (Margin below this page) Example 24 The compound in Table IN08 was added to a normal nematic liquid crystal crude product.
% was added and the helical pitch was measured, it was 65
1 0.2 μII1 at °C, 8.9 at 44'C
μm, and the temperature change is small (it was found that it can be effectively used for preventing reverse domains in TN liquid crystals, STN liquid crystals, etc. [Effects of the Invention] Compounds of general formula (I) of the present invention In the case where the chiral dopant is added as all or a part of the chiral dopant to the parent Sc liquid crystal compound or compound to form an Sc" liquid crystal compound, a small amount of addition induces large spontaneous polarization. With such a structure, the viscosity can be kept low, and the reaction time can be several tens of microseconds, which is less than 1/100 of that of conventional nematic liquid crystals, making it suitable as a material for liquid crystal devices. It is extremely useful. Also, in terms of the helical pitch, especially in the N0 phase, it is possible to obtain both a compound with a relatively large helical pitch, which facilitates pitch adjustment, and a compound with a small helical pitch, which is used for adjusting the helical pitch, etc. As a result, the Sc''&ll compound of the present invention has very good orientation.
In addition, compounds with a small helical pitch can be used in addition to conventional TN liquid crystals to prevent so-called reverse domains.
Furthermore, it can be suitably used for STM liquid crystals, etc.
Further, the compound of the present invention can be easily produced industrially by the production method provided by the present invention. Furthermore, it is colorless and has excellent chemical stability against light, water, heat, etc., making it very practical. January 24, 1990 Patent applicant Dainippon Ink & Chemicals Co., Ltd. Kawamura Physical and Chemical Research Institute

Claims (1)

[Claims] 1. An optically active compound 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 20 carbon atoms, or any one of these alkyl groups, or 2 that are not adjacent to each other.
or 3 -CH_2- are unsubstituted or -O-, ▲ there is a mathematical formula, chemical formula, table, etc. ▼ ▲ there is a mathematical formula, chemical formula, table, etc. ▼ or -CH=N- is substituted, and any one to 2 C's
H_2 is unsubstituted or ▲There is a mathematical formula, chemical formula, table, etc.▼
, Y_1 and Y_2 are each independently H, F,
Represents any one of Cl, CH_3, CF_3, OCH_3, CN, and when an asymmetric carbon is produced by substitution, the absolute configuration of the asymmetric carbon is at least one of (R) and (S), and any CH_2, CH_3 are unsubstituted or CF_2
, represents a group substituted with CF_3, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ each independently represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Any 1 to 4 -CH= in these rings are each independently is unsubstituted or substituted with ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼, and X is -F, -Cl, -CH_3, -CN, -CF_3 or -
Represents OCH_3, and any one or two CH_2 are unsubstituted or each independently substituted with ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and one or two non-adjacent -CH_2- are unsubstituted or - O-or-
Replaced with S-, any ▲There is a mathematical formula, chemical formula, table, etc.▼ is unsubstituted or replaced with ▲There is a mathematical formula, chemical formula, table, etc.▼, and X^1 is -F, -Cr, -CH_3, - C.N.
, -CF_3 or -OCH_3, Z_1 and Z
_2 are each independently COO, OCO, CH_2O,
OCH_2, CH_2CH_2, -C≡C-, -C-C
H_2-, -CH_2-C- or a single bond, m represents 0 or 1, and R^2 is any one alkyl group having 1 to 15 carbon atoms or 2 to 3 non-adjacent C
H_2 is unsubstituted or substituted with -O-, and any 1 to
Three CH_2 are unsubstituted or each independently ▲ Formula,
There are chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. and C^* is (R
) or (S) configuration asymmetric carbon atom. ) 2. R1 is an alkyl group, alkoxyl group, alkoxycarbonyl group, or alkanoyloxy group having 1 to 20 carbon atoms, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ respectively Independently, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, which represents X^2,
X^3 each independently represents F, CN, or H, and at least one of them is F or CN, and Z_1 and Z_2 each independently represent COO, OCO, CH_2O, OCH_2
The optically active compound according to claim 1, which represents a single bond or a single bond. 3, R^1 is a linear alkyl group having 1 to 20 carbon atoms,
It is a linear alkoxyl group or a branched optically active alkoxyl group, and ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ both ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ , Z^1 and Z^2 each independently represent a single bond, -COO- or -OC
3. The optically active compound according to claim 2, wherein R^2 is O- and R^2 is a linear alkyl group, a branched optically active alkyl group, or a branched optically active alkoxyalkyl group having 1 to 15 carbon atoms. 4. The optically active compound according to claim 3, wherein m is 0. 5. The optically active compound according to claim 4, wherein Z^1 is -COO-. 6. The optically active compound according to claim 5, wherein R^1 is a linear alkoxyl group having 1 to 20 carbon atoms, and R^2 is a linear alkyl group having 1 to 15 carbon atoms. 7, R^1 is n-C_1_0H_2_1O-, and C
^* is an asymmetric carbon atom with (R) configuration, and R^2 is n-
The optically active compound according to claim 6, which is C_4H_9-. 8. The optically active compound according to claim 5, wherein R^1 is a linear alkoxyl group having 1 to 20 carbon atoms, and R^2 is a branched optically active alkyl group having 1 to 15 carbon atoms. 9, R^1 is n-C_1_0H_2_0O-, and C
9. The optically active compound according to claim 8, wherein ^* is an asymmetric carbon atom with the (R) configuration, and R^2 is ▲ where there is a numerical formula, chemical formula, table, etc. ▼. 10, R^1 is n-C_1_0H_2_1O-,
9. The optically active compound according to claim 8, wherein C^* is an asymmetric carbon atom in the (S) configuration, and R^2 is ▲ where there is a numerical formula, chemical formula, table, etc. ▼. 11, R^2 is the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, l and m each independently represent an integer from 0 to 5, and R^3 is a carbon atom represents an alkyl group of numbers 1 to 10,
C^*^* represents an asymmetric carbon atom of (R) or (S) configuration. ) The optically active compound according to claim 5, which is an optically active group represented by: 12, R^1 is n-C_1_0H_2_1O-,
12. The optically active compound according to claim 11, wherein C^* is an asymmetric carbon atom with the (R) configuration, and R^2 is ▲a formula, a chemical formula, a table, etc. ▼. 13, R^1 is n-C_1_0H_2_1O-,
12. The optically active compound according to claim 11, wherein C^* is an asymmetric carbon atom with (S) configuration, and R^2 is ▲formula, chemical formula, table, etc.▼. 14. The optically active compound according to claim 4, wherein Z^1 is OCO. 15. The optically active compound according to claim 14, wherein R^1 is a linear alkoxyl group having 1 to 20 carbon atoms, and R^2 is a linear alkyl group having 1 to 15 carbon atoms. 16, R^1 is n-C_8H_1_7O-, and C^
* is an asymmetric carbon atom with (S) configuration, and R^2 is n-C
The optically active compound according to claim 15, which is _5H_1_1-. 17. The optically active compound according to claim 3, wherein m is 1. 18. Claim 17, wherein Z^1 and Z^2 are both single bonds.
The optically active compound described. 19. The optically active compound according to claim 18, wherein R^1 is a linear alkyl group having 1 to 20 carbon atoms, and R^2 is a branched optically active alkyl group having 1 to 15 carbon atoms. 20, R^1 is n-C_5H_1_1-, and C^*
20. The optically active compound according to claim 19, wherein is an asymmetric carbon atom with an (S) configuration, and R^2 is ▲a numerical formula, a chemical formula, a table, etc. ▼. 21. The optically active compound according to claim 17, wherein Z^1 is a single bond and Z^2 is -COO-. 22. The optically active compound according to claim 21, wherein R^1 is a linear alkyl group having 1 to 20 carbon atoms, and R^2 is a linear alkyl group having 1 to 15 carbon atoms. 23, R^1 is n-C_8H_1_7-, and C^*
is an asymmetric carbon atom with (R) configuration, and R^2 is n-C_
The optically active compound according to claim 22, which is 4H_9-. 24. The optically active compound according to claim 21, wherein R^1 is a branched optically active alkoxyl group having 1 to 20 carbon atoms, and R^2 is a linear alkyl group having 1 to 15 carbon atoms. 25, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
25. The optically active compound according to claim 24, which is an asymmetric carbon atom having the R) configuration, and R^2 is n-C_4H_9. 26, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
25. The optically active compound according to claim 24, which is an asymmetric carbon atom having the R) configuration, and R^2 is n-C_4H_9. 27. The optically active compound according to claim 21, wherein R^1 is a linear alkyl group having 1 to 20 carbon atoms, and R^2 is a branched optically active alkyl group having 1 to 15 carbon atoms. 28, R^1 is n-C_8H_1_7-, and C^*
28. The optically active compound according to claim 27, wherein is an asymmetric carbon atom having an (R) configuration, and R^2 is ▲a formula, a chemical formula, a table, etc. ▼. 29. The optically active compound according to claim 21, wherein R^1 is a branched optically active alkoxyl group having 1 to 20 carbon atoms, and R^2 is a branched optically active alkyl group having 1 to 15 carbon atoms. 30, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
30. The optically active compound according to claim 29, which is an optically active group having the S) configuration, and R^2 is ▲, which has a mathematical formula, a chemical formula, a table, etc. 31, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
30. The optically active compound according to claim 29, which is an optically active group having the S) configuration, and R^2 is ▲, which has a mathematical formula, a chemical formula, a table, etc. 32. The optically active compound according to claim 29, wherein R^2 is an optically active group represented by the general formula (II) according to claim 11. 33, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
33. The optically active compound according to claim 32, which is an optically active group having the S) configuration, and R^2 is ▲ where there is a numerical formula, chemical formula, table, etc. ▼. 34. The optically active compound according to claim 21, wherein R^1 is a branched optically active alkoxyl group having 1 to 20 carbon atoms, and R^2 is a formula, a chemical formula, a table, etc. 35, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
35. The optically active compound according to claim 34, which is an optically active group having the R) configuration, and R^2 is ▲, which has a numerical formula, a chemical formula, a table, etc. 36, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C^* is (
35. The optically active compound according to claim 34, which is an optically active group having the S) configuration, and R^2 is ▲ where there is a numerical formula, chemical formula, table, etc. ▼. 37. The optically active compound according to claim 21, wherein R^1 is a linear alkoxyl group having 1 to 20 carbon atoms, and R^2 is a linear alkyl group having 1 to 15 carbon atoms. 38, R^1 is n-C_8H_1_7O-, and C^
* is an asymmetric carbon atom with (R) configuration, and R^2 is n-C
38. The optically active compound according to claim 37, which is _5H_1_1-. 39, R^1 is n-C_8H_1_7O-, and C^
* is an asymmetric carbon atom with (R) configuration, and R^2 is n-C
38. The optically active compound according to claim 37, which is _4H_9-. 40. The optically active compound according to claim 21, wherein R^1 is a linear alkoxyl group having 1 to 20 carbon atoms, and R^2 is a branched optically active alkyl group having 1 to 15 carbon atoms. 41, R^1 is n-C_8H_1_7O-, and C^
41. The optically active compound according to claim 40, wherein * is an asymmetric carbon atom with the (R) configuration, and R^2 is ▲ where there is a numerical formula, chemical formula, table, etc. ▼. 42. A liquid crystal composition containing the optically active compound according to any one of claims 1 to 41. 43. The liquid crystal composition according to claim 42, which exhibits a chiral smectic phase. 44. A ferroelectric liquid crystal display element using the liquid crystal composition according to claim 42. 45. General formula (III) below ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ m represents the same thing as stated in claim 2.) A compound represented by is reacted with trimethylsilyl cyanide in the presence of a Lewis acid and an optically active diol, and the following general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (wherein, ▲mathematical formulas, chemical formulas) , tables, etc. ▼ m represents the same as the above general formula (III), and C^* represents an asymmetric carbon atom in the (S) or (R) configuration.) An optically active cyanohydrin derivative represented by A claim characterized in that this is reacted with a carboxylic acid represented by R^2COOH represented by the general formula (V) (wherein R^2 represents the same thing as in claim 1). 2. The method for producing an optically active compound according to 2.