JPH02256638A - Optically active compound, liquid crystal composition containing the compound and liquid crystal light-modulation apparatus using the liquid crystal composition - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is 3-14C alkyl, alkenyl or alkynyl; R2 is 1-10C alkyl, 2-10C alkenyl or alkynyl: group of formula II is 5- to 8-membered ring; Q1 is single bond, (thio)ether bond, carboxylic acid ester bond, carbonyl bond, etc.; Q2 and Q3 are Q1 or methyleneoxy bond; M is group of formula III or formula IV (X and Y are single bond, carboxylic acid ester, methyleneoxy or ethylene group; the rings A to C are 6-membered ring-1,4-diyl)]. EXAMPLE:cis-(1R,2S)-2-methoxycyclopentane-1-carboxylic acid 4'-octyloxy-4- biphenyl ester. USE:A ferroelectric liquid crystal compound having high spontaneous polarization. It has excellent quick response and memorizing characteristics. PREPARATION:A compound of formula I wherein Q2 is normal ester bond [-C(=O)-O-] can be produced e.g. by reacting a carboxylic acid of formula V with an optically active dichiral alcohol of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel optically active compound and a liquid crystal composition containing the compound. In particular, the present invention provides liquid crystal materials exhibiting ferroelectric liquid crystals, such as optically active compounds useful in liquid crystal light modulators as electro-optic switching elements such as liquid crystal display elements, liquid crystal compositions containing the compounds, and liquid crystal compositions containing the compounds. A liquid crystal light modulator using a liquid crystal composition containing a compound is provided.

[Prior Art] Liquid crystal display elements have excellent characteristics such as low voltage operation, low power consumption, thinness and lightness, and light-receiving type that does not cause eye fatigue, so they are widely used as various display devices. used in

Currently, Twisted Nematlc type (T
A liquid crystal display device using a nematic liquid crystal called an N-type liquid crystal is used. However, display devices using this nematic liquid crystal cannot be used with other light-emitting display devices, such as CRTS.
It had the disadvantage that the response was very slow compared to EL and the like. Furthermore, when this nematic liquid crystal display device is applied to a large screen display with a large amount of display information, its contrast is low due to insufficient threshold characteristics, which limits its wide range of applications. Recently, 5uper Tvl
stedNesatlc (S T N type) or S
A nematic liquid crystal display device called BE has been discovered that has improved threshold characteristics and improved contrast. However, even in the STN type liquid crystal display, there is little improvement in response, and there is a limit to its application to displays that display a larger amount of information. For this reason, various attempts have been made to develop new liquid crystal display systems that can be applied to large-screen displays that display a large amount of information.

Since ferroelectric liquid crystals exhibit memory functions and high-speed response, there are great expectations for their application to large-screen displays. Chiral smectic C phase, chiral smectic H, J phase, etc. are known as liquid crystals exhibiting ferroelectricity, but ferroelectric liquid crystal exhibiting chiral smectic cm is considered to be particularly practical. Ferroelectric liquid crystals exhibiting a chiral smectic C phase were first synthesized in 1975 by R.B. -Methyl butyl ester (hereinafter abbreviated as DOBAMBC) [J, Phys.
lque, 36. L-69 (1975)].

N, A, C1ark et al. created a thin-film type liquid crystal cell using this DOBAMBC, and achieved high-speed response and memory performance on the μSee order [N, A.

C1ark et al., Appl, Phys, Let
t,,36. 89. (1980)].

This led to the development of liquid crystal display elements, optical printer heads, and other light modulation elements using ferroelectric liquid crystals exhibiting a chiral smectic C phase (hereinafter sometimes simply referred to as ferroelectric liquid crystals). Ta.

Therefore, many ferroelectric liquid crystal compounds exhibiting a chiral smectic C phase have been developed since then, and various ferroelectric liquid crystal compounds are now known. However, a ferroelectric liquid crystal compound that has sufficient reliability and performance to manufacture large-screen displays using ferroelectric liquid crystals has not yet been found.

[Question 8 to be solved by the invention] In order to put ferroelectric liquid crystal into practical use as a liquid crystal display element, etc.
It is necessary to have high-speed response, good orientation, memory properties, threshold properties, and low temperature dependence of these properties. Further, in order to be able to operate in a sufficiently wide temperature range including room temperature, it is necessary that the temperature range in which the chiral smectic C phase is exhibited is wide, and that the material has excellent physical and chemical stability.

Among these, it is particularly important that the material be physically and chemically stable, and that it exhibits stable high-speed response and memory properties.

According to experiments by C1ark et al., it has been reported that a μSee-order response is possible under certain conditions. However, even if a large screen display with a large amount of display information, that is, an extremely large number of pixels, can be realized under the conditions of C1ark et al., it is desired that the response of the display be even faster.

The response time (τ) of a ferroelectric liquid crystal is approximately given by the following formula, ignoring the torque caused by the dielectric anisotropy and the external electric field, τ−η/P s E (τ; response time, η; Viscosity coefficient, PS; Spontaneous polarization, E;
(Applied electric field) Expansion of spontaneous polarization is effective for high-speed response.

On the other hand, it is thought that the memory property improves depending on the value of spontaneous polarization. Increasing the spontaneous polarization increases the polarization electric field, which stabilizes the state where the dipole moments are aligned, that is, stabilizes the memory state.

Increasing spontaneous polarization in this way is very effective in simultaneously solving two problems specific to ferroelectric liquid crystals. From this point of view, recent efforts have been made to develop ferroelectric liquid crystal compounds for the purpose of increasing spontaneous polarization. For example, as a physicochemically stable compound, (R) or (S)-1
Ester-based ferroelectric liquid crystal compounds using -methylbutanol or (R) or (S)-1-methylheptatool as an optically active group have been reported [K.

Tcrashlma Ctal,, Hot, Cr
yst, Liq, Cryst,.

141.237 (1986)]. Although the spontaneous polarization of these compounds is relatively large at 50 nC/am'' or more, it is still not sufficient.

Therefore, in order to further increase the spontaneous polarization, a compound having two asymmetric carbon atoms as an optically active group essential for the appearance of the chiral smectic C phase was synthesized. For example, liquid crystal compounds with dichiral epoxide side chains [Walbe et al.
Journal of American Chemical φ Society, 108°7424 (1986)] or liquid crystal compounds having a halogen atom and a methyl group on the adjacent asymmetric carbon (Japanese Patent Application Laid-open No. 168780, 1986, 2183 No.
58, 61-68449, 62-40, 62-4
6, 62-103043, 62-111950, 62-142131, 62-175443, etc.)
etc. can be mentioned.

A typical example is 4'-octylcarbonyloxy-4
-Biphenyl(S)-3-methyl-2-chloropentanoate (JP-A-61-68449). This liquid crystal compound exhibits a very large spontaneous polarization of 180 nC/mark 2. However, since it is an aliphatic chlorine compound, it has poor chemical stability.

Therefore, 4'-octylcarbonyloxy-4-[(S)-2-methoxy-(S)-3-
Methylpentyloxycarbonyl]biphenyl (JP-A-62-228036) has been synthesized. However, a compound that has a small spontaneous polarization of 17 nC/(to)2, is chemically stable, and has a large spontaneous polarization has not yet been developed.

[Means for Solving the Problems] The present inventors conducted various studies in order to find a ferroelectric liquid crystal compound with excellent physical and chemical stability and large spontaneous polarization, and arrived at the present invention. That is, for a liquid crystal compound that combines a chemically stable ester compound and an optically active group with two asymmetric carbon atoms, we investigated the correlation between the chemical structure of the optically active group and spontaneous polarization, and based on the results. The present invention was arrived at.

The spontaneous polarization of ferroelectric liquid crystals is based on the dipole moment of the ether group or carbonate group adjacent to the asymmetric carbon. When a polar group such as an ether group or a carboxylic acid ester group is bonded to each of two asymmetric carbons, the mutual relationship between the dipole moment vectors of the two polar groups becomes important.

That is, it was found that fixing the conformation of the two polar groups (preventing free rotation of the bond between the two asymmetric carbon atoms) is effective in increasing spontaneous polarization.

In this way, by fixing the conformation of the polar group on the asymmetric carbon, we succeeded in increasing spontaneous polarization without using a halogen-carbon bond, which has poor chemical stability.

That is, the present invention has the following formula: 10 alkenyl group or alkynyl group, *, --1・* 10 〇- represents a hetero atom other than carbon or a double bond i
Q represents a single bond, (thio)ether bond, carboxylic acid ester bond, carbonyl bond, carbonyldioxy bond, Q2 and Q
3 represents a single bond, (thio)ether bond, carboxylic acid ester bond, carbonyl bond, carbonyl dioxy bond, or methyleneoxy bond, respectively, and M is Single bond, carboxylic acid ester bond,
Indicates a methyleneoxy bond or an ethylene bond, −()
, () -+ represents a homologous or heterologous six-membered ring-1,4-diyl group which may each have 1 or 2 oxygen atoms or nitrogen atoms as ring constituent atoms. Further, carbons marked with * mean asymmetric carbons. Note that the hydrogen atom bonded to the asymmetric carbon atom may be substituted with a lower alkyl group having 1 to 6 carbon atoms or a lower alkenyl group having 2 to 6 carbon atoms. ] This relates to optically active compound 13 represented by:

The present liquid crystal compound [1] has the essential properties as a ferroelectric liquid crystal compound regardless of the conformation of the polar group on the asymmetric carbon in the cyclic part. It is characterized by the appearance of a large spontaneous polarization when the polar groups adopt a conformation in the same direction.

For example, the conformation of two polar groups on the asymmetric carbon of the ring part is
If two phase-adjacent asymmetric carbons are used to form a five-membered ring, etc., and Q2 and Q3 are positioned in the same direction in the plane of the ring, that is, in a cis configuration, the dipole moment of Q2 and Q3 is The vectors point in the same direction, resulting in a large spontaneous polarization. That is, a first aspect of the present invention relates to a liquid crystal compound having a large spontaneous polarization, a second aspect to a liquid crystal composition containing at least one optically active compound, and a third aspect to a liquid crystal composition containing at least one optically active compound. The present invention relates to a liquid crystal light modulator using the liquid crystal composition.

Compound [1] according to the first aspect of the present invention has a basic skeleton M
Based on this, the following compounds can be divided into [I'] and [■'].

The alkyl group having 3 to 14 carbon atoms represented by R1 in the above compounds [1], [1'], and [I'] may be linear or branched, and specifically, for example, , propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, etc., such as isopropyl, isobutyl, 5ee-butyl,
tert-butyl, isopentyl, neopentyl, te
rt-pentyl, isohexyl, 1-methylpentyl,
2-methylpentyl, 5-methylhexyl, 2,3.5
Branched alkyl groups such as -trimethylhexyl, 2.7.8-trimethyldecyl, and 4-ethyl-5-methylnonyl can be mentioned. Among them, it is linear and has 6 carbon atoms.
-12 alkyl groups are preferred, such as hexyl, heptyl, octyl, decyl, undecyl, dodecyl.

Examples of the alkenyl group and alkynyl group include those corresponding to the above-mentioned alkyl groups.

The 1-10 alkyl group represented by R2 may be linear or branched, and specifically includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Straight chain alkyl groups such as nonyl, decyl, and also for example isopropyl, isobutyl, 5ee-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl,
Branched alkyl groups such as 1-methylpentyl, 2-methylpentyl, 5-methylhexyl, 4-ethylhexyl, 2,3.5-trimethylhexyl, and 4-ethyl-5-methylhexyl are mentioned. Among these, linear alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, are preferred.

Examples of the alkenyl group and alkynyl group include those corresponding to the above-mentioned alkyl groups.

Ql, Q2, and Q3 represent a single bond, a (thio)ether bond, a carboxylic acid ester bond, a carbonyl bond, a carbonyldioxane bond, or a methyleneoxy bond.

As a carboxylic acid ester bond, A reverse ester bond can be mentioned.

Furthermore, examples of the methyleneoxy bond include a -CH20- bond and a -0CH2- bond.

Among various combinations of Q1 to Q3, Ql is preferable.
is a single bond, (thio)ether bond or forward ester bond, Q2 is a forward ester, reverse ester or ether bond,
Examples of Q3 include (thio)ether bond, forward ester or reverse ester include -0-C-, and examples of methyleneoxy bond include -CF2O- and -0CH2-. be able to.

Furthermore, the six-membered ring-1 represented by -(), -(E)-, +
,4-diyl group, specifically, for example, p-phenylene, 1,4-cyclohexylene, 2.5-(1,3
-dioxane)diyl, 2°5-pyridinediyl, 2.
Examples include 5-pyrimidinediyl, 2.5-(1,4-pyrazine)diyl, 3.6-(1,2-pyridazine)diyl, etc., and these rings are substituted with halogen, cyano, methyl, or methoxy. may have been done. Also(),(
) + may be the same or different.

can.
2.5-(1,3-dioxane)diyl bond Also, the carboxylic acid ester bond shown by XSY.
．． As the bonding mode of 5-pyridinediyl, there can be mentioned two types of bonding modes of 2.5-pyrimidinediyl.

A preferred combination is that one of X1Y is a single bond and the other is a carboxylic acid ester bond, and
Both + are p-phenylene, or at least one is 2,5-pyrimidinediyl.

In addition, when M is represented by +X+, a preferable combination is one in which X is a single bond and both -+ and -e are p-phenylene or one of them is 2,5-pyrimidinediyl. be able to.

These compounds [I] have two asymmetric carbon atoms in the molecule, and therefore have four types of optical isomers, namely (R
,R), (R,S), (S, R) and (S
, S) type exists.

The above compound [1] of the present invention can be produced, for example, by the method shown below.

Method 1: Compound where Q2 is an ester bond (-C-0-), R1-Q, -M-COOH [■] [R1, R2, Ql, Q3 and M have the same meanings as above. The same applies hereafter] As shown in FIG. 1 above, compound [1] can be obtained by subjecting carboxylic acid [■] and optically active dichiral alcohol [ml] to a condensation reaction.

In this condensation reaction, the reaction itself is known and can be carried out using conventional means. For example, carboxylic acid [II] and dichiral alcohol [I[[]
are subjected to a condensation reaction in an organic solvent in the presence of a protic acid. Examples of protonic acids include inorganic acids such as sulfuric acid, hydrochloric acid, and perchloric acid, organic sulfonic acids such as p-)luenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and methanesulfonic acid, or Amberlyst Co., Ltd. A strongly acidic ion exchange resin such as the following can be used. In addition, examples of organic solvents include hydrocarbons (hexane,
benzene, toluene, etc.), halogenated hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, 1゜2-dichloroethane, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), ethyl acetate, acetonitrile, dimethylformamide, etc. Can be used. Carboxylic acid [, For example, the reaction may be carried out in the presence of a tertiary amine such as pyridine or triethylamine. Alternatively, after introducing alcohol [ml] into trimethylsilyl ether derivative *7---.* [Me Si -0-C,9-Q3-R2], this and the acid halogenated derivative of carboxylic acid [II] were combined. Condensation can also be carried out in the presence of Lewis acids (eg zinc chloride).

In addition, free reagents such as N,N-dicyclohexylcarbodiimide (DCC), 1-methyl-2-halopyridinium iodide, diethyl ester of azodicarboxylic acid (DEAD) and triphenylphosphine (Ph3P) are also used. The reaction between carboxylic acid [■] and alcohol [ml] can also proceed using a combination of (so-called Mitsunobu's reagent) or an activating reagent such as triphenylphosphine dibromide.

These methods are described, for example, in Journal Organic Chemistry 27.4675 (1962); Tetrahedron Letters, 1978.4475;
Letter, 1975, 1045; Chemistry Letter,
1976.13. Bulletin Φ Chemical Society Japan.

50.1863 (1977) Bulletin Chemical ψ
Society◆Japan, 40.2380 (1967)
:Synthetic Communication, 16.142
3 (1986); Synthetic Communication, 16, 659 (1986).

Method 2: Compound where Q2 is a reverse ester bond (-0-C-) Figure 2 R1-Ql-M-OH [IV] As shown in Figure 2 above, a hydroxyl group-containing compound [IV] and an optically active dichiral carbon Compound [I] can be obtained by subjecting it to a condensation reaction with acid [V]. In this condensation reaction, the reaction itself is a known reaction, and the reaction can be carried out using the above-mentioned conventional means.

Method 3: Compound where Q2 is an ether bond (-0-) Figure 3 R, -Q, -M-OH [IV] R-Q -M-0-C, C-Q3-R2 [I] Above figure 3 As shown in the figure, compound [1] can be obtained by subjecting hydroxyl group-containing compound [IV] and optically active dichiral alcohol [II] to an etherification reaction.

In this etherification reaction, the reaction itself is a known reaction, and the reaction can be carried out using conventional means. For example, azodicarboxylic acid diethyl ester (
DEAD) and triphenylphosphine (Ph3P) (Pittner et al.).

Chemical Fist and Industries, 1975°28
1). Alternatively, the corresponding organic sulfonic acid ester can be obtained by reacting dichiral alcohol [m] with an organic sulfonyl chloride in an organic solvent in the presence of an organic base such as pyridine or triethylamine or an inorganic base such as sodium hydride. , this ester is converted into a hydroxyl group-containing compound [I
V]. This reaction is carried out in an organic solvent in the presence of an inorganic base such as potassium carbonate or sodium hydride, or an organic base such as pyridine or triethylamine. Examples of the organic sulfonyl chloride that can be used in this reaction include p-toluenesulfonic acid chloride, o-toluenesulfonic acid chloride, p-chlorobenzenesulfonic acid chloride, benzenesulfonic acid chloride, α-naphthalenesulfonic acid chloride, β- Examples include aromatic ring sulfonic acid chlorides such as naphthalene sulfonic acid chloride, and aliphatic sulfonic acid chlorides such as methanesulfonic acid chloride and trifluoromethanesulfonic acid chloride.

Examples of organic solvents that can be used in this etherification reaction include aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, etc.), Ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), ethyl acetate, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DM
SO), hexamethylphosphate triamide (HMPA)
etc.

Dichiral alcohol [111] during the etherification reaction
In addition to the above-mentioned sulfonic acid esterification method, there is a method for activating halogen derivatives. For example, a metal halide salt (
It can be converted into a halogen by reacting with sodium iodide, potassium iodide, etc. Alternatively, a halogenating agent such as phosphorus pentachloride, thionyl chloride, thionyl bromide, etc. may be directly applied to the dichiral alcohol [III]. The halogen compound thus obtained and the hydroxyl group-containing compound [IVl] can be reacted in an organic solvent in the presence of the above-mentioned inorganic base or organic base.

In addition, Q2 also represents a single bond, carbonyl bond, carbonyldioxy bond, or methyleneoxy bond,
All of these can be manufactured using conventional means.

The target product [I] produced by the above method is separated and purified from the reaction solution using commonly used separation and purification means, such as extraction, dissolution, column chromatography, liquid chromatography, and recrystallization. be able to.

The starting materials [11], [ml, [IVl], [V] for producing the optically active compound [I] of the present invention are all known substances or can be easily derived from known substances. I can do it. For example, the optically active dichiral compounds [I[I], [V] are new compounds, but they can be derived from known optically active dichiral compounds, and are particularly suitable for asymmetric synthesis by chemical methods (Morrison et al. Volumes 1 (1983) to 5 (1985) S Bosnich et al., Asymmetric Catalysis (1986); Shatter et al., Anti-Syn, 1983.939), Asymmetric Synthesis by Biological Methods Using Enzymes and Microorganisms [Jones etc.

“Applications of Biochemical Systems and Organic Chemistry” John Wiley, New York (1976); Fretzter et al.
Tetrahedron, 40.1269 (1984); Hoffmann et al., Chemische Beliichte, 114.2786
(1981); Nashimura et al. Tetrahedron Letters, 27.3155 (1986)], optical splitting [Yakkouz et al.

“Enantiomers Red Semates and Resolutions” John Willey and Sons (1981);
Ingersoll, Organic Fist Synthesis, Collective Volume, 2,506 (1943); Nohei,
Chemistry φ Letters, 1981, 875, 951]
It can also be obtained by methods such as The dichiral compound (III) (V) thus obtained is:
It is also possible to convert to other optical isomers by inverting the configuration on the asymmetric carbon by chemical or biological methods. For example, a typical method for inverting the hydroxyl group of an optically active secondary alcohol is to convert the hydroxyl group into a corresponding organic sulfonic acid ester and then invert it by subjecting it to a molecular nucleophilic substitution reaction [Coray et al.

Tetrahedron Letters, 1975.3183゜Sawyer and Gibbian, Tetrahedron, 35゜1471
(1979); Kruisinga et al., Journal Organic Chemistry, 46.4321 (1981
): Hoffmann and Desai, Synthetic Communication, 13, 553 (1978)], or an optically active secondary alcohol is mixed with N,N in the presence of cuprous chloride.
- A method of activating with dicyclohexylcarbodiimide (DCC) and then inverting it by acting with an appropriate carboxylic acid [Kauren, Angewantehemii 99.
800 (1987)], or diethyl ester of azodicarboxylic acid (DEA) in an optically active secondary alcohol.
D), triphenylphosphine < p h s
P) and a method of inversion by the action of an appropriate carboxylic acid [Mitsunobu and Eguchi, Bulletin Chemical Co., Ltd.
Society Japan.

44.3427 (1971); Mitsunobu, Synthesis, 1981, 11, etc. are known.

In optically active dichiral secondary alcohol [III] and optically active dichiral carboxylic acid [V], which are important raw materials for constituting the dichiral moiety of the optically active compound of the present invention, *7---・*10 〇 - is a 5- to 8-membered alicyclic compound, W other than carbon
It is a cyclic compound containing a bo atom or a cyclic compound having a double bond.

In addition, these cyclic compounds contain not only asymmetric carbon atoms but also
Other ring-constituting atoms may also have substituents such as lower alkyl groups having 1 to 6 carbon atoms and alkenyl groups having 2 to 6 carbon atoms.

*7--・Moon 10 When 0- is an alicyclic compound, the cyclic group may be any 5-membered ring, but preferably a 5- or 6-membered ring is selected. More specifically, the general formula is as follows.

m, n: an integer of 1 to 6, 3≦m+n≦6 However, for example, in the above formula, if m”n and there is no substituent in the cyclic group, the carbon atom marked with * does not become an asymmetric carbon, and therefore the present invention Excluded from compounds.

*7---・* When =CC- is an alicyclic compound, general formula [III] and θ
Examples of the compound represented by "-"[V] include the following.

Examples of optically active dichiral secondary alcohols include when Q3 is an ether bond (-0-): (R2''=C1-10 alkyl) (2-alkyloxycyclopentanol) More specific examples of such compounds include For example, 2-methoxycyclopentanol, 2-ethoxycyclopentanol, 2-propoxycyclopentanol, 2-butoxycyclopentanol, 2-pentyloxycyclopentanol, 2-hexyloxycyclopentanol, 2-
Linear alkyloxycyclopentanol such as hebutyloxycyclopentanol, 2-octyloxycyclopentanol, 2-nonyloxycyclopentanol, 2-decyloxycyclopentanol or 2-isopropoxycyclopentanol, 2 Branched alkyloxycyclopenes such as -isobutoxycyclopentanol, 2-tert-butoxycyclopentanol, 2-(2-methylpentyloxy)cyclopentanol, 2-(3-methylpentyloxy)cyclopentanol, etc. Tanol can be mentioned.

More specifically, such compounds include, for example,
2-methoxycyclohexanol, 2-ethoxycyclohexanol, 2-propoxycyclohexanol, 2
-butoxycyclohexanol, 2-pentyloxycyclohexanol, 2-hexyloxycyclohexanol, 2-hebutyloxycyclohexanol, 2-octyloxycyclohexanol, 2-nonyloxycyclohexanol, 2-decyloxycyclohexanol, etc. Linear alkyloxycyclohexanol, or 2-isopropoxycyclohexanol, 2-isobutoxycyclohexanol, 2-tert-butoxycyclohexanol, 2-(2-methylpentyloxy)cyclohexanol, 2-(3-methyl Branched alkyloxycyclohexanols such as pentyloxy)cyclohexanol can be mentioned.

(R2'=C1-10 alkyl) (2-alkyloxycyclohexanol) Zero * Branched alkyloxycycloheptatools such as butanol can be mentioned.

(Alkyl of R2 simple C1-10) (2-alkyloxycycloheptatool) More specifically, such compounds include, for example, 2-methoxycycloheptatool, 2-ethoxycycloheptanol, 2-propoxycyclo Heptanol, 2-butoxycycloheptanol, 2-pentyloxycycloheptanol, 2-hexyloxycycloheptanol, 2-
Linear alkyloxycycloheptatools such as hebutyloxycycloheptanol, 2-octyloxycycloheptatool, 2-nonyloxycycloheptanol, 2-decyloxycycloheptanol, or 2-isopropoxycycloheptanol, 2-isobutoxycycloheptanol, 2-tert-butoxycycloheptanol, 2-(2-methylpentyloxy)cycloheptatool, 2-(3-methylpentyloxy)cyclo(R2san C1-10 alkyl ( 2-alkyloxycycloophthal) More specifically, such compounds include, for example, 2-methoxycycloophthal, 2-ethoxycycloophthal, 2-ethoxycycloophthal,
-proboxycyclooctal, 2-butoxycycloophthal, 2-pentyloxycycloophthal, 2-
Linear alkyloxycycloophthal such as hexyloxyofcour, 2-heptyloxyoccour, 2-octyloxycycloophthal, 2-nonyloxycycloophthal, 2-decyloxycycloophthal,
Or 2-isopropoxycyclooctyl, 2-isobutoxycycloophthal, 2-tert-butoxycycloofcoeur, 2-(2-methylpentyloxy)cyclooctyl, 2-(3-methylpentyloxy)cycloofcoeur Mention may be made of branched alkyloxycyclophthal such as tar. Further, (R2■alkyl of Cl-10) (3-alkyloxycyclopentanol) More specifically, such compounds include 3-methoxycyclopentanol, 3-ethoxycyclopentanol, 3-
Propoxycyclopentanol, 3-butoxycyclopentanol, 3-pentyloxycyclopentanol,
3-hexyloxycyclopentanol, 3-hebutyloxycyclopentanol, 3-octyloxycyclopentanol, 3-nonyloxycyclopentanol,
Linear alkyloxycyclopentanol such as 3-decyloxycycloheptanol, or 3-isopropoxycyclopentanol, 3-isobutoxycyclopentanol, 3-tert-butoxycyclopentanol, 3-(2-methyl Branched alkyloxycyclopentanol such as pentyloxy)cyclopentanol and 3-(3-methylpentyloxy)cyclopentanol can be mentioned.

Regarding homologs of other alicyclic compounds, similar derivatives can be exemplified as specific examples.

For example, (R21IIICl-lo alkyl) (3-alkyloxycyclohexanol) (R2''Cl-to alkyl) (3-alkyloxycycloheptatool) Also, Q3 is a reverse ester bond (-0-C-) Case: (R2=Cl-10 alkyl) (3-alkyloxycycloophthal) (R2mCI
-1o alkyl) (2-acyloxycyclopentanol) (R2”Cl
-10 alkyl) (4-alkyloxycycloheptatool) (R2”=
Cl-10 alkyl) (2-acyloxycyclohexanol) (R2”Cl
-10 alkyl) (4-alkyloxycycloophthal) (R2=Cl
-10 alkyl) etc. can be mentioned as a typical example.

(2-acyloxycycloheptanol) (R2-C1
-10 alkyl) (R2 Cl-10 alkyl) ((2-acyloxycycloophthal)alkyl ester of 2-hydroxyoxycyclohexanoic acid) etc. can be mentioned as specific examples.

Case: (R2 group C1-10 alkyl) (2-hydroxycyclohebutanoic acid alkyl ester) (R2=Cl-10 alkyl (2-hydroxyoxycyclopentanoic acid alkyl ester) (R2 "C1-10 alkyl Specific examples include alkyl) (alkyl, ester of 2-hydroxycyclooctanoic acid).

Moreover, the following can be mentioned as an example of the optically active cyclic dichiral carboxylic acid [V].

(Alkyl(2-alkyloxycyclopentanecarboxylic acid) where R2=Cl-10) More specifically, such compounds include, for example, 2-
Methoxycyclopentanecarboxylic acid, 2-ethoxycyclopentanecarboxylic acid, 2-propoxycyclopentanecarboxylic acid, 2-butoxycyclopentanecarboxylic acid,
2-pentyloxycyclopentanecarboxylic acid, 2-hexyloxycyclopentanecarboxylic acid, 2-hebutyloxycyclopentanecarboxylic acid, 2-octyloxycyclopentanecarboxylic acid, 2-nonyloxycyclopentanecarboxylic acid, 2- Linear alkyloxycyclopentanecarboxylic acid such as decyloxycyclopentanecarboxylic acid, or 2-isopropoxycyclopentanecarboxylic acid, 2-isobutoxycyclopentanecarboxylic acid, 2-tert-butoxycyclopentanecarboxylic acid,
Branched alkyloxycyclopentanecarboxylic acids such as 2-(2-methylpentyloxy)cyclopentanecarboxylic acid and 2-C3-methylpentyloxy)cyclopentanecarboxylic acid can be mentioned.

(Alkyl of R2''Cl-to) (2-alkyloxycyclohexanecarboxylic acid) More specifically, such compounds include, for example, 2-
Methoxycyclohexanecarboxylic acid, 2-ethoxycyclohexanecarboxylic acid, 2-propoxycyclohexanecarboxylic acid, 2-butoxycyclohexanecarboxylic acid,
2-pentyloxycyclohexanecarboxylic acid, 2-hexyloxycyclohexanecarboxylic acid, 2-hebutyloxycyclohexanecarboxylic acid, 2-octyloxycyclohexanecarboxylic acid, 2-nonyloxycyclohexanecarboxylic acid, 2-decyloxycyclohexanecarboxylic acid, etc. linear alkyloxycyclohexanecarboxylic acid, or 2-isopropoxycyclohexanecarboxylic acid, 2-isobutoxycyclohexanecarboxylic acid, 2-tert-butoxycyclohexanecarboxylic acid,
Branched alkyloxycyclohexanecarboxylic acids such as 2-(2-methylpentyloxy)cyclohexanecarboxylic acid and 2-(3-methylpentyloxy)cyclohexanecarboxylic acid can be mentioned.

(R2-Cl-10 alkyl(2-alkyloxycyclohebutanecarboxylic acid)) More specifically, such compounds include, for example, 2-
Methoxycyclohebutanecarboxylic acid, 2-ethoxycyclohebutanecarboxylic acid, 2-propoxycyclohebutanecarboxylic acid, 2-butoxycyclohebutanecarboxylic acid,
2-pentyloxycyclohebutanecarboxylic acid, 2-hexyloxycyclohebutanecarboxylic acid, 2-hebutyloxycyclohebutanecarboxylic acid, 2-octyloxycyclohebutanecarboxylic acid, 2-nonyloxycyclohebutanecarboxylic acid acids, linear alkyloxycycloheptatools such as 2-decyloxycycloheptancarboxylic acid, or 2-isopropoxycyclohebutanecarboxylic acid, 2-isobutoxycyclohebutanecarboxylic acid, 2-decyloxycycloheptancarboxylic acid, etc.
- tert-butoxycyclohebutanecarboxylic acid, 2
- Branched alkyloxycyclohebutanecarboxylic acids such as (2-methylpentyloxy)cyclohebutanecarboxylic acid and 2-(3-methylpentyloxy)cyclohebutanecarboxylic acid can be mentioned.

(R2''C1-10 alkyl) (2-alkyloxycyclooctanecarboxylic acid) More specifically, such compounds include, for example, 2-
Methoxycyclooctanecarboxylic acid, 2-ethoxycyclooctanecarboxylic acid, 2-propoxycyclooctanecarboxylic acid, 2-butoxycyclooctanecarboxylic acid,
2-pentyloxycyclooctanecarboxylic acid, 2-hexyloxycyclooctanecarboxylic acid, 2-hebutyloxycyclooctanecarboxylic acid, 2-octyloxycyclooctanecarboxylic acid, 2-nonyloxycyclooctanecarboxylic acid, 2-decyl Linear alkyloxycyclooctanecarboxylic acid such as oxycyclooctanecarboxylic acid, or 2-isopropoxycyclooctanecarboxylic acid, 2-isobutoxycyclooctanecarboxylic acid, 2-tert-butoxycyclooctanecarboxylic acid,
Branched alkyloxycyclooctanecarboxylic acids such as 2-(2-methylpentyloxy)cyclooctanecarboxylic acid and 2-(3-methylpentyloxy)cyclooctanecarboxylic acid can be mentioned.

Next, when Q3 is a reverse ester bond (-0-C-): (R2""alkyl of L-1o) (2-acyloxycyclopentanecarboxylic acid) (R2
”=Cl-10 alkyl) (2-acyloxycyclohexanecarboxylic acid) (R2
"C1-10 alkyl) (2-acyloxycyclohebutanecarboxylic acid) (R2
Specific examples include "alkyl of Cl-10" (2-alkyloxycarbonylcyclopentanecarboxylic acid) (alkyl of R2-C1-10) (2-acyloxycyclooctanecarboxylic acid).

In addition, when Q3 is an ester bond (-C-0-): (R2=alkyl of Cl-10) (2-alkyloxycarbonylcyclohexanecarboxylic acid) (R2''=alkyl of Cl-10) (2-alkyl Typical examples include (oxycarbonylcyclohebutanecarboxylic acid) (R2=alkyl of Ct-to) (2-alkyloxycarbonylcyclooctanecarboxylic acid).

In addition, compounds represented by the following formula can also be mentioned.

(Alkyl of R2m-C1-1o) (3-alkyloxycyclopentanecarboxylic acid) More specifically, as such a compound, for example, 3-
Methoxycyclopencunecarboxylic acid, 3-ethoxycyclopentanecarboxylic acid, 3-propoxycyclopencunecarboxylic acid, 3-butoxycyclopentanecarboxylic acid,
3-pentyloxycyclopentanecarboxylic acid, 3-hexyloxycyclopentanecarboxylic acid, 3-hebutyloxycyclopentanecarboxylic acid, 3-octyloxycyclopentanecarboxylic acid, 3-nonyloxycyclopentanecarboxylic acid, 3- Linear alkyloxycyclopentanecarboxylic acid such as decyloxycyclopentanecarboxylic acid, or 3-isopropodicyclopentanecarboxylic acid, 3-isobutoxycyclopentanecarboxylic acid, 3-tert-butoxycyclopentanecarboxylic acid,
Branched alkyloxycyclobencune carboxylic acids such as 3-(2-methylpentyloxy)cyclopentanecarboxylic acid and 3-(3-methylpentyloxy)cyclopentanecarboxylic acid can be mentioned.

Regarding homologs of other alicyclic compounds, similar derivatives can be exemplified as specific examples. For example, when Q3 is a reverse ester bond <-5-o->: (R2 cod 9t-to alkyl (3-alkyloxycyclohexanecarboxylic acid) (R
2-llICl-lo alkyl) (3-acyloxycyclopentanecarboxylic acid) (R2 ■ C1-10 alkyl) (3-alkyloxycyclohebutanecarboxylic acid) (R
2111ICl-lo alkyl) (3-acyloxycyclohexanecarboxylic acid) (R2 "Cl-10 alkyl) (3-alkyloxycyclooctanecarboxylic acid) (R
2 San C1-10 alkyl) (3-acyloxycyclohebutanecarboxylic acid) (R2
Specific examples include mC1-10 alkyl) (3-acyloxycyclooctanecarboxylic acid).

Next, when Q3 is a forward ester bond <-C-O->: (R2-01-1o alkyl) (3-alkyloxycarbonylcyclopentanecarboxylic acid) (R2=CL-10 alkyl) (3- Alkyloxycarbonylcyclohexanecarboxylic acid) (R2-1-C1-10 alkyl) (3-alkyloxycarbonylcyclohebutanecarboxylic acid) (R2''=C1-10 alkyl) (3-alkyloxycarbonylcyclooctanecarboxylic acid) ) etc. can be cited as specific examples.

In addition, when Q3 is an ether bond (-0-): (R2''
= C1-10 alkyl) (4-alkyloxycyclohebutanecarboxylic acid) (R
2”=C1-10 alkyl) (4-acyloxycyclohebutanecarboxylic acid) (R2
""1-10 alkyl) (4-alkyloxycyclooctanecarboxylic acid) Q3
When is a reverse ester bond (-0-C-): (R2''C1-10 alkyl) (4-acyloxycyclooctanecarboxylic acid) etc. can be mentioned as a specific example.

When Q3 is a forward ester bond (-C-0-): (R2"C1-10 alkyl) (4-alkyloxycarbonylcyclohebutanecarboxylic acid) υ (R2"C1-10 alkyl) (4-acyloxy Specific examples include cyclooctanecarboxylic acid).

*7--~, *10 In the case of a 5- to 8-membered monocyclic compound in which C- contains a heteroatom other than carbon, the heteroatom is S or 0
can be mentioned.

*7--・* When -CC- is a heterocyclic ξ compound containing a heteroatom other than carbon, the compounds represented by general formulas [IV] and [V] are, for example, the following: can give.

*7--* When -CC- is a 5-membered ring containing a different atom other than carbon, such as a sulfur atom, and Q is an ether bond (-0-), the following examples can be given.

(Alkyl of R2''Cl-10) (4-alkyloxytetrahydrothiophen-3-ol) More specifically, such compounds include, for example,
4-methoxytetrahydrothiophene-3-ol, 4
-ethoxytetrahydrothiophene-3-ol, 4-
Propoxytetrahydrothiophene-3-ol, 4-
Butoxytetrahydrothiophene-3-ol, 4-pentyloxytetrahydrothiophene-3-ol, 4
-hexyloxytetrahydrothiophene-3-ol, 4-hebutyloxytetrahydrothiophene-3-ol, 4-octyloxytetrahydrothiophene-3
-ol, 4-nonyloxytetrahydrothiophene-
Linear 4-alkyloxytetrahydrothiophene-3-ol such as 3-ol, 4-decyloxytetrahydrothiophene-3-ol, or 4-isopropoxytetrahydrothiophene-3-ol, 4-isobutoxytetrahydrothiophene-3 -all, 4-ter
t-Butoxytetrahydrothiophene-3-ol, 4
-(2-methylpentyloxy)tetrahydrothiophen-3-ol, 4-(3-methylpentyloxy)
Branched 4-alkyloxytetrahydrothiophene-3-ols such as tetrahydrothiophene-3-ol can be mentioned.

When Q3 is an ester bond (-C-0-), the following examples can be given.

(Alkyl of R2-01-10) (4-Hydroxytetrahydrothiophene-3-carboxylic acid alkyl ester) More specifically, such compounds include, for example,
4-hydroxytetrahydrothiophene-3-carboxylic acid methyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid ethyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid propyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid Butyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid pentyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid hexyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid hexyl ester, 4-hydroxytetrahydrothiophene-3 - Linear alkyl ester derivatives such as carboxylic acid octyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid nonyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid decyl ester, or 4-hydroxytetrahydrothiophene-3-carboxylic acid acid isopropyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid isobutyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid tert-butyl ester, 4-hydroxytetrahydrothiophene-3-carboxylic acid 2-methylpentyl ester, 4- Branched alkyl ester derivatives such as hydroxytetrahydrothiophene-3-carboxylic acid 3-methylpentyl ester can be mentioned.

*Do-.* Another example is also given when =CC- is a 5-membered ring containing a sulfur atom and Q3 is a forward ester bond (-C-0-).

(R2''=alkyl of Cl-10) (3-hydroxytetrahydrothiophene-2-carboxylic acid alkyl ester) More specifically, such compounds include, for example,
3-Hydroxytetrahydrothiophene-2-carboxylic acid methyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid ethyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid propyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid butyl ester Esters, 3-hydroxytetrahydrothiophene-2-carboxylic acid pentyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid hexyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid octyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid Acid nonyl ester, linear alkyl ester derivatives such as 3-hydroxytetrahydrothiophene-2-carboxylic acid decyl ester, or 3-hydroxytetrahydrothiophene=2
-carboxylic acid isopropyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid isobutyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid tert-butyl ester, 3-hydroxytetrahydrothiophene-2-carboxylic acid 2-methylpentyl ester, Branched alkyl ester derivatives such as 3-hydroxytetrahydrothiophene-2-carboxylic acid 3-methylpentyl ester can be mentioned.

*7---・* 10 When 0- is a 5-membered ring containing a sulfur atom and Q3 is a reverse ester bond (-0-C-), the following examples can also be given.

(Alkyl of R2-CI-10) (4-acyloxytetrahydrothiophen-3-ol) More specifically, such compounds include, for example,
4-acetyloxytetrahydrothiophene-3-ol, 4-propionyloxytetrahydrothiophene-
3-ol, 4-butyryloxytetrahydrothiophene-3-ol, 4-valeryloxytetrahydrothiophene-3-ol, 4-hexanoyloxytetrahydrothiophene-3-ol, 4-heptanoyloxytetrahydrothiophene-3 -ol, 4-octanoyloxytetrahydrothiophene-3-ol, 4-nonanoyloxytetrahydrothiophene-3-ol-
Linear acyloxy derivatives such as 4-decanoyloxytetrahydrothiophene-3-ol, or 4-isobutyryloxytetrahydrothiophene-3-ol,
4-isovaleryloxytetrahydrothiophene-3-
ol, 4-pivaloyloxytetrahydrothiophene-3-ol, 4-(2-methylpentanoyloxy)tetrahydrothiophene-3-ol, 4-(3-methylpentanoyloxy)tetrahydrothiophene-3
-branched acyloxy derivatives such as -ol.

Although examples of optically active cyclic secondary alcohols as raw materials have been given above, there are no specific limitations to these. For example, a similar example can be given when -CC- is a 5-membered ring containing a highly oxidized sulfur atom, i.e. 8'yh-jrad or 8ruhotz (R2"C1-1
alkyl of 0; n-1 or 2) (R2 = alkyl of Cl-10 *7--, * An example of [m] is =C C- is a 5-membered ring containing a sulfur atom, and Q is an atom-f Specifically, we take the case of a double bond, a similar ester bond, or a reverse ester bond as an example (R2 ``CI-
10 alkyl; n-1 or 2) . That is, (R2 “alkyl of CI-10; n-1 or 2)*
7--, ne=C When C- is a 6-membered ring containing a sulfur atom, a derivative similar to ε can be given as an example (R2 ``CI
-alkyl of to) can.

Book, -m-・Book Also, -〇 C- is a carbon atom, a heteroatom other than a sulfur atom, "MJ-t" is a 5- or 6-membered ring containing oxygen (R2
Similar derivatives can be cited as examples for "alkyl of 1-10".

*7ーー・* 10 If C- is a 5- to 8-membered cyclic system containing a double bond, '
For t#-m L <, a 5- or 6-membered cyclic system is selected.

At this time, the number of double bonds is not limited, but is up to 1 (R2
"Alkyl of CI-10" or those having two double bonds are preferred.

Particularly preferred examples are shown below.

(R2-Alkyl of Cl-10) (R2=Alkyl of Cl-10) (Same meanings as above for Q3 and R2) (R2ImCI
-1o alkyl) Book, -1・* In addition, examples in the case where -〇〇- is a 6-membered ring containing a double bond are listed below.

(Q3, R2 have the same meanings as above) (Q3, R2 have the same meanings as above) (Q3, R2 have the same meanings as above) Regarding the optically active cyclic secondary alcohol [m], R2 is Cl-10. Although the example of alkyl was illustrated, R2
The same applies to the case of alkenyl or alkynyl where is 02-10, and of course it is not limited to the above example.

The other important raw material is optically active cyclic carboxylic acid [V]
Examples include: Even in the case of aqueous systems, it is not limited to these examples.

*Do-, *10 When C- is a 5-membered ring containing a different atom other than a carbon atom, such as a sulfur atom, and Q is an ether bond (-0-), the following examples can be given: .

(R2-1-C1-10 alkyl) (4-alkyloxytetrahydrothiophene 3-carboxylic acid) More specifically, such compounds include, for example,
4-methoxytetrahydrothiophene-3-carboxylic acid, 4-ethoxytetrahydrothiophene-3-carboxylic acid, 4-propoxytetrahydrothiophene-3-carboxylic acid, 4-butoxytetrahydrothiophene-3-carboxylic acid, 4-pentyloxytetrahydrothiophene -3-carboxylic acid, 4-hexyloxytetrahydrothiophene-3-carboxylic acid, 4-hebutyloxytetrahydrothiophene-3-carboxylic acid, 4-octyloxytetrahydrothiophene-3-carboxylic acid, 4-nonyloxytetrahydrothiophene- 3-carboxylic acid, 4
linear alkyloxy derivatives such as -decyloxytetrahydrothiophene-3-carboxylic acid, or 4-isopropoxytetrahydrothiophene-3-carboxylic acid,
4-isobutoxytetrahydrothiophene-3-carboxylic acid, 4-1ert-butoxytetrahydrothiophene-3-carboxylic acid, 4-(2-methylpentyloxy)
Tetrahydrothiophene-3-carboxylic acid, 4-(3
-methylpentyloxy)tetrahydrothiophene-3
-branched alkyloxy derivatives such as carboxylic acids.

(R2''1-10 alkyl) (3-alkyloxytetrahydrothiophene-2-carboxylic acid) For example, 3-methoxytetrahydrothiothiophene-2-carboxylic acid, 3-ethoxytetrahydrothiophene-2-
Carboxylic acid, 3-propoxytetrahydrothiophene-
2-carboxylic acid, 3-butoxytetrahydrothiophene-2-carboxylic acid, 3-pentyloxytetrahydrothiophene-2-carboxylic acid, 3-hexyloxytetrahydrothiophene-2-carboxylic acid, 3-hebutyloxytetrahydrothiophene-2 -carboxylic acid, 3-octyloxytetrahydrothiophene-2-carboxylic acid, 3-nonyloxytetrahydrothiophene-2-carboxylic acid, 3-decyloxytetrahydrothiophene-2
-Linear alkyloxy derivatives such as carboxylic acid, or 3-isopropoxytetrahydrothiophene-2-carboxylic acid, 3-isobutoxytetrahydrothiophene-
2-carboxylic acid, 3-tert-butoxytetrahydrothiophene-2-carboxylic acid, 3-(2-methylpentyloxy)tetrahydrothiophene-2-carboxylic acid, 3-(3-methylpentyloxy)tetrahydrothiophene-2-carboxylic acid Branched alkyloxy derivatives such as acids can be mentioned.

When -m-*=CC- is a 5-membered ring containing a sulfur atom and Q3 is an ester bond (-C-0-), the following examples can be given.

(Alkyl of R2IllC1-1o) (4-alkyloxycarbonyltetrahydrothiophene-3-carboxylic acid) More specifically, such compounds include, for example,
4-methoxycarbonyltetrahydrothiophene-3-
Carboxylic acid, 4-ethoxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-propoxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-butoxycarbonyltetrahydrothiophene-3-carboxylic acid,
4-Pentyloxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-hexyloxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-hebutyloxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-octyloxycarbonyltetrahydrothiophene-3 -carboxylic acid, linear alkyloxycarbonyl derivatives such as 4-nonyloxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-decyloxycarbonyltetrahydrothiophene-3-carboxylic acid, or 4-isopropoxycarbonyltetrahydrothiophene-3- Carboxylic acid, 4-isobutoxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-tert
-Butoxycarbonyltetrahydrothiophene-3-carboxylic acid, 4-(2-methylpentyloxy)carbonyltetrahydrothiophene-3-carboxylic acid, 4-(
Branched alkyloxycarbonyl derivatives such as 3-methylpentyloxy)carbonyltetrahydrothiophene-3-carboxylic acid can be mentioned.

*, ---1* 10 When 0- is a 5-membered ring containing a sulfur atom and Q3 is an ester bond (-C-0-), the following examples may also be given.

(R2=Cl-10 alkyl) (2-alkyloxycarbonyltetrahydrothiophene-3-carboxylic acid) (R2"Cl-10 alkyl) (3-alkyloxycarbonyltetrahydrothiophene-3-carboxylic acid) *7-- , when N is a reverse ester bond (-0-C-), the following examples can also be given.

(R2""1-10 alkyl) (4-acyloxytetrahydrothiophene-3-carboxylic acid) More specifically, such compounds include, for example,
4-acetyloxytetrahydrothiophene-3-carboxylic acid, 4-propionyloxytetrahydrothiophene-3-carboxylic acid, 4-butyryloxytetrahydrothiophene-3-carboxylic acid, 4-valeryloxytetrahydrothiophene-3-carboxylic acid, 4-heptanoyloxytetrahydrothiophene-3-carboxylic acid, 4
- Linear acyloxy derivatives such as octanoyloxytetrahydrothiophene-3-carboxylic acid, 4-nonanoyloxytetrahydrothiophene-3-carboxylic acid, 4-decanoyloxytetrahydrothiophene-3-carboxylic acid, or 4-isobutyloxy Ryloxytetrahydrothiophene-3-carboxylic acid, 4-isovaleryloxytetrahydrothiophene-3-carboxylic acid, 4-pivaloyloxytetrahydrothiophene-3-carboxylic acid,
Branched acyloxy derivatives such as 4-(2-methylpentanoyloxy)tetrahydrothiophene-3-carboxylic acid and 4-(3methylpentanoyloxy)tetrahydrothiophene-3-carboxylic acid are mentioned.

Another example is also given when *7---.* is a reverse ester bond (-0-C-).

(R2""1-10 alkyl) (3-acyloxytetrahydrothiophene 2-carboxylic acid) More specifically, such compounds include, for example,
3-acetyloxytetrahydrothiophene-2-carboxylic acid, 3-propionyloxytetrahydrothiophene-2-carboxylic acid, 3-butyryloxytetrahydrothiophene-2-carboxylic acid, 3-valeryloxytetrahydrothiophene-2-carboxylic acid, 3-heptanoyloxytetrahydrothiophene-2-carboxylic acid, 3
- Linear acyloxy derivatives such as octanoyloxytetrahydrothiophene-2-carboxylic acid, 3-nonanoyloxytetrahydrothiophene-2-carboxylic acid, 3-decanoyloxytetrahydrothiophene-2-carboxylic acid, or 3-isobutyryl Oxytetrahydrothiophene-2-carboxylic acid, 3-isovaleryloxytetrahydrothiophene-2-carboxylic acid, 3-pivaloyloxytetrahydrothiophene-2-carboxylic acid, 3
Branched acyloxy derivatives such as -(2-methylpentanoyloxy)tetrahydrothiophene-2-carboxylic acid and 3-(3-methylpentanoyloxy)tetrahydrothiophene-2-carboxylic acid are mentioned.

Although the optically active cyclic carboxylic acid [V] used as a raw material has been specifically illustrated above, it is not limited to *, -m-* and these specific examples. For example, when -CC- is a 5-membered ring containing a highly oxidized sulfur atom, ie, sulfoxide or sulfone, the following similar examples can be given.

(R2”C1-10 alkyl; n=m1 or 2)
(R2''C1-1o alkyl; n-1 or 2) (R
2'' Alkyl chain of Cl-10, -m-, *=C When C- is a 6-membered ring containing a sulfur atom, a similar derivative can be cited as an example.

(R2 ``Alkyl of CI-10 - *, ---, * Also, for a 5- or 6-membered ring in which -〇 C- contains a carbon atom or a different atom other than a sulfur atom, such as oxygen, similar derivatives are used as examples) I can list many things.

(R2 = Cl-10 alkyl; n-1 or 2)*
7--*Furthermore, in the case where -C C- is a 5-membered ring containing a double bond, C-like derivatives can be cited as an example. That is, (R2 "alkyl of CI-to; n-1 or 2) (
R2 = Cl-10 alkyl) (R2-Cl-10 alkyl) (R2-Cl-to alkyl) (R2 ``Cl-10 alkyl) (R2-Cl-10 alkyl) (For Q3, R2 (same meaning as above) (R2
10 alkyl) (Q3, R2 have the same meanings as above) (Q3, R2 have the same meanings as above) (Q3, R2 have the same meanings as above) In the above, R for optically active cyclic carboxylic acid [V] Although the example of C alkyl is illustrated, the same applies when R22L-10 is C2-10 alkenyl or alkynyl, and of course it is not limited to the above example.

The above-mentioned optically active cyclic compounds include novel compounds represented by the following formula.

Book 2--*Z-C,C-Q3-R2 [wherein, R2 is an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms]
~10 alkenyl group or alkynyl group, Q3 represents a single bond, (thio)ether bond, carbonyl bond, methyleneoxy bond, and 2 represents a hydroxyl group or a cooz' group (
However, 2' represents hydrogen or an alkyl group having 2 to 10 carbon atoms), and *7--~・*-CC- may be a hetero atom other than carbon or a double bond. Indicates a member ring. ] These compounds are usually synthesized by a known method according to the route shown below.

・-1 Me1 That is, known compound a was prepared by a known method using baker's yeast [B
, S. Doel et al., Au5t, J. Chew,
, 29. 2459 (1976), and then the obtained compound C is subjected to an alkylation reaction to obtain compound C, which is further hydrolyzed. Compound d is thereby obtained. Other compounds are also produced by known methods.

Compounds c, d, e, l, m, o and p are novel and useful as intermediates for the liquid crystal compounds of the present invention.

In addition, the optically active cyclic compound is a method of hydrolyzing a brochiral cyclic 1°2-diester using an enzyme CM, 5chn
Eider et al., Angev Chew, 1ntern
at, Ed.

Engl., 23.67 (1984)].

ψ1 Compound Y is also a known compound, which is asymmetrically reduced,
Then, using this product, the following compounds are produced by known means.

Compounds t, u,

Incidentally, the optically active cyclic compound can be prepared by the following method for preparing the brochiral compound [for example, 5akal et al., Cheta.

Common, 838 (1987) and 966 (
1988) by a known method.

The following compound can be produced by a known method by subjecting Compound m, which is a known compound, to asymmetric reduction and using the obtained substance.

Compounds 1v and vlii are novel and useful as intermediates for the liquid crystal compounds of the present invention.

The optically active dichiral cyclic secondary alcohol [III] and the optically active cyclic dichiral carboxylic acid [V] are specifically exemplified above, but Q3 is a single bond, thioether bond, carbonyl bond, carbonyldioxy bond, or methyleneoxy bond Similar cyclic derivatives can also be used in other cases, and the invention is not limited to the above-mentioned specific examples.

Next, carboxylic acid [11] and alcohol or phenolic hydroxyl group-containing compound [IV], which are important raw materials for constructing the skeleton of the optically active compound of the present invention, will be specifically explained by giving representative examples. .

Raw material carboxylic acid [1] can be roughly classified into compounds represented by the following general formula.

[■' ] Such compounds include, for example, 4-(4'alkyloxy or alkyl-4-biphenylcarbonyloxy)
Benzoic acid, 4-(4'-alkyloxy or alkyl-4-biphenyloxycarbonyl)benzoic acid, 4'
-(4-alkyloxy or alkylphenylcarbonyloxy)-4-biphenylcarboxylic acid, 4' -(4
-alkyloxy or alkylphenyloxycarbonyl)-4-biphenylcarboxylic acid. Furthermore, for example 4-alkyloxy or alkyl-4-biphenylcarboxylic acids, 4'-alkyloxy (or alkyl)-
4-terphenylcarboxylic acid, 4'-(trans-4-
alkyloxy or alkylcyclohexylcarbonyloxy)-4-biphenylcarboxylic acid, trans-4-
(4'-alkyloxy or alkyl-4-biphenylcarbonyloxy)cyclohexylcarboxylic acid, 2-
[4-(4-alkyloxy or alkylphenylcarbonyloxy)phenyl]pyrimidinyl-5-carboxylic acid, 2-(4'-alkyloxy or alkyl-4
-biphenyl)pyrimidinyl-5-carboxylic acid, 4'
-(5-alkyloxy or alkylpyrimidinyl-2
-oxycarbonyl)biphenyl-4-carboxylic acid, 4
' -[2-(5-alkyloxy or alkyl-2-
pyridyl)ethyl]biphenyl-4-carboxylic acid, 4-
[4-(trans-5-alkyloxy or alkyl-
1,3-dioxan-2-yl)phenylcarbonyloxy]benzoic acid, 4'-[4-(trans-5-alkyloxy or alkyl-1,3-dioxan-2-yl)]]biphenyl-4-carboxylic acid or for example 2-[4-(4-furkyloxy or alkylphenylcarbonyloxy)phenyl]pyrazinyl-5-carboxylic acid, 2-(4'-alkyloxy or alkyl-4
-biphenyl)pyrazinyl-5-carboxylic acid, 4'(5
-furkyloxy or alkylpyrazinyl-2-oxycarbonyl)biphenyl-4-carbonylic acid, 4' -
(6-alkyloxy or alkyl-3-pyridazinyl)biphenyl-4-carboxylic acid and the like can be mentioned.

Further, the raw material compound (1) can be roughly classified into compounds represented by the following general formula.

[■'] Such compounds include, for example, 4-hydroxyphenyl ester of 4'-alkyloxy or alkylbiphenyl-4-carboxylic acid, 4-hydroxyphenyl ester of 4'-hydroxybenzoic acid,
'-alkyloxy or alkyl-4-biphenyl ester, 4' of 4-alkyloxy or alkylbenzoic acid
-hydroxy-4-biphenyester, 4-alkyloxy or alkylphenyl ester of 4'-hydroxybiphenyl-4-carboxylic acid, and the like. Furthermore, for example 4'-hydroxy-4-biphenyl esters of trans-4-alkyloxy or alkylcyclohexanecarboxylic acids, trans-4-hydroxycyclohexyl esters of 4'-alkyloxy or alkyl-4-biphenylcarboxylic acids, 4-alkyl 4-(5-hydroxy-2-pyrimidinyl)phenyl esters of oxy- or alkylbenzoic acids, 2-(4'-alkyloxy or alkyl-4-biphenyl)pyrimidin-5-ols,
5-alkyloxy or alkyl-2-pyridinyl ester of 4'-hydroxy-4-biphenylcarboxylic acid,
4'-[2-(5-alkyloxy or alkyl-2
-pyridyl)ethyl]biphenyl-4-ol, 4-
[4-(trans-5-alkyloxy or alkyl-
1,3-dioxan-2-yl)] 4-hydroxyphenyl ester of benzoic acid, 5-alkyloxy or 5-alkyl-2-pyrazinyl ester of 4'-hydroxy-4-biphenylcarboxylic acid, etc. can.

Since the optically active compound [II of the present invention has a structure in which an asymmetric carbon atom is bonded to oxygen or carbonyl,
Generally exhibits high spontaneous polarization. Also, most of the compounds are
In addition to exhibiting a liquid crystal phase suitable for display systems that utilize ferroelectricity, that is, a chiral smectic C (Sc) phase,
It has the characteristic that its temperature range is low and wide.

Furthermore, the optically active compound of the present invention is extremely stable against heat, light, moisture, and air. Therefore, when using the compound of the present application as a liquid crystal material, it is necessary to install a heating prevention device, prevent moisture absorption,
It is possible to eliminate the need for a frit seal or the like to prevent moisture permeation.

The optically active compound [11] of the present invention has excellent compatibility with conventionally known liquid crystal compounds, such as Schiff base-based, biphenyl-based, phenylcyclohexane-based, and heterocyclic-based liquid crystal compounds, and therefore can be incorporated into these liquid crystal compounds. By doing so, a liquid crystal composition exhibiting excellent properties can be obtained.

Examples of liquid crystal compounds to which the optically active compound [II of the present invention can be blended include ferroelectric liquid crystal compounds and liquid crystal compounds exhibiting a smectic C phase. As a ferroelectric liquid crystal compound, for example, JP-A-59-
1187144, biphenyl type liquid crystal described in JP-A No. 60-13729, JP-A-59-128357, JP-A-60-13729.
0-51147, 61-22051, 61-249
Ester type liquid crystal described in Publication No. 953, JP-A-60
-260564, 61-24756, 61-853
Examples include pyrimidine liquid crystals described in 68 and 61-215373. In addition, examples of liquid crystal compounds exhibiting a smectic C phase include, for example, JP-A-62-2
The ester-type liquid crystal compound described in Publication No. 28036, the 16th Freiburg Liquid Crystal Symposium (1986, March 2)
1) and the cyclohexane type and heterocyclic type liquid crystals described in the materials of the 1st International Symposium on Ferroelectric Liquid Crystals (1984, September 21).

Furthermore, the optically active compound of the present invention is a “liquid crystal table”.
I and II (VEB Verlag, Lelp
It can also be blended into nematic liquid crystals, cholesteric liquid crystals, etc. described in J. zig), and can also be blended with commercially available nematic liquid crystals. In particular, when the optically active compound of the present invention is blended into a nematic liquid crystal, the twist direction and pitch length of the cholesteric pitch of the nematic liquid crystal composition can be freely controlled.

When the optically active compound of the present invention is blended with other liquid crystals as described above, the blending ratio may be selected depending on the purpose. For example, when producing a ferroelectric liquid crystal composition, the optically active compound of the present invention is added in an amount of 5 to 50% by weight based on the total amount of the composition.
If a nematic liquid crystal composition is prepared, it may be blended in an amount of 0.1 to 5% by weight. Further, a liquid crystal composition may be constructed using only the optically active compound of the present invention.

Liquid crystal light modulation devices include various display devices using multiple liquid crystal display elements, such as word processors, display devices such as laptop personal computer workstations, image display devices such as televisions and video telephones, and optical communication device terminals. Examples include display boards.

Although various types of liquid crystal display elements are known, any display element may be used as long as the liquid crystal composition according to the present invention can effectively exhibit its performance. for example,
Such a display element is disclosed in U.S. Pat. No. 4.367.924.
No. 63-22287, U.S. Patent No. 4,563
, No. 059, etc., can be effectively used.

The basic configuration of these elements is usually a pair of substrates,
It consists of a polarizer provided on the substrate, a pair of transparent electrodes, a pair of molecular alignment layers, a liquid crystal composition sealed between the pair of substrates by a peripheral sealing material, and a reflective plate.

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

The phase series, phase transition temperature, and spontaneous polarization value of the optically active compounds produced in Examples were measured. The measurement results are summarized in Table 1 together with the elemental analysis values.

Note that the phase series and phase transition temperature were measured using a polarizing microscope and a differential thermal capacitance meter (DSC).

Further, spontaneous polarization was measured according to the above-mentioned Sawyer-Tower method. The value of spontaneous polarization is chiral smectic C
This is the value at a temperature 10°C lower than the upper limit temperature of the phase.

Each phase such as the liquid crystal phase is indicated by the following symbols.

I: Tokichi phase Ch: Cholesterits phase O 8A: Smectic A phase K: Crystalline phase *.

Sc, chiral smectic C phase St, S2: Smectic phase difficult to identify Example 1 cis-(IR,2S)-2-methoxycyclopentane-
4'-octyloxy-4-biphenyl of 1-carboxylic acid (in formula [I'], R1 is n-CHR is CH3, Q
(1) Production of cis-(IR,23)-2-methoxycyclopentane-1-carboxylic acid Synthesis The present optically active cyclic dichiral carboxylic acid can be produced by the following route. That is, the literature method using baker's yeast to prepare 2-oxynecyclopentane-1-carboxylic acid ethyl ester [B, S, Dole et al., Au5t, J, C
hct, 29.2459 (1976)], and then the obtained cis-(IR928)-2-
The title compound is prepared by subjecting hydroxycyclopentane-1-carboxylic acid ethyl ester to a methylation reaction followed by an acidic hydrolysis reaction. Crystal IR and 1H-N
The MR spectrum is shown below.

H'H-NMR (90 MI'lz, CD CD a ) δ
: 1.42, 25 (6H, m, CR2), 2.6-
3.05 (IH, m, >CHCOO).

3, 35 (3H1s, OCHs), 3.85-4
, 15 (I H,m, >CHOCH3).

7, 7-8.6 (IH, broads, Co2H
) The 1H-NMR spectrum of the ethyl ester (colorless oil) of the title compound is also shown below.

'H-NMR (90MIZ, CDC1) 3) δ: 1.
26(3H,t,J-7,5)1z,OCH2Cdan3
).

1.3 2-3 (6H1m, CH2), 2.6-3
．． 1 (IH,m, ,CdanCo2Et).

3,28 (3H,s, OHa), 3.8-4-
4 (3Hlm, CHOCHa and/Co20H2CH3) (ii) Esterification reaction 4'-octyloxy-4-biphenol (0,,68
g) and pyridine (0.6 ml) in dry tetrahydrofuran (10 ml) was added the cis-(
IR,2S)-2-Methoxycyclopentane-1-carboxylic acid (472,5ωg) was treated with oxalyl chloride to produce acid chloride, dried toluene (5.0ml)
The solution was added at room temperature with stirring. After stirring at room temperature for 4 days, the reaction solution was concentrated under reduced pressure, and benzene was added to the residue. Insoluble materials were removed by filtration, and the filtrate was concentrated under reduced pressure.

The residue was subjected to column chromatography using silica gel (150 g) and carbon tetrachloride-ether (10:1). The title compound (0.44 g) was obtained as waxy crystals from the desired fraction. IR of the crystal, 'H -NMR spectrum is shown below.

IRν""Lam-': 1755, 1500, 124
5゜1lax 1210, 1165'HNMR (90MHz, CD C1) a) δ: 0
．． 89 (3H, t, J=6Hz.

-CH2C Dan 3), 1.0-2.5 (18H.

m, CH2), 2-9 3.4 (IH, m.

>CH-Coo), 3.39 (3H, s.

0CHa ) = 3t 99 (2H, t, J-
6Hz.

0CR2), 3.9 4.25 (LH, m.

〉Cdan-0CH3), 6.75-7.6　(8H.

m1 aromatic H) Example 2 cis-(IR,2S)-2-methoxycyclopentane-
4-(4'-octyloxy-4- of 1-carboxylic acid)
biphenyloxycarbonyl) phenyl ester (formula [
■'], Rt is n Cs Hl 7, R2 is C
H3, Ql and Q3 are -0-1 Q2 is ster (in formula [I']) R1 is n Cs
Hty, R2 is CH3, Ql and Q3 are single bonds,
Production of cis-(IR,2S)-2-methoxycyclopentane-1-carboxylic acid chloride 1f (3
82.5 mg) and 4-(4'-octyloxy-4-
biphenyloxycarbonyl)phenol (0,95g
) to obtain the title compound (0.65 g) as a colorless powder product (recrystallized from ethanol).

Example 3 cis-(IR,2S)-2-methoxycyclopenkune-1-carboxylic acid 4'-(4-octyloxyphenyloxycarbonyl)-4-bihuesha and +sha are respectively →H ) Production of cis-(IR,2S)-2-methoxycyclopentane-1-carboxylic acid chloride (38
2,5 mg) and 4-octyloxyphenyl ester of 47-hydroxy-4-biphenylcarboxylic acid (0,9
The title compound (0.51 g) was obtained as colorless needle crystals (recrystallized from ethanol).

Example 4 Cis-(IR,2S)-2-methoxycyclobencune-
4'-(4-octyloxyphenyloxycarbonyloxy)-4-biphenyl ester of 1-carboxylic acid (in formula [I']) R1 is n-CHR is CHQ and Q3 is 8 17ゝ 2 3ゝ 1 phenyl Ester (in formula [■']) Rt is n-Cs H17, R2
cis-(IR,2S)-2-methoxycyclopentane-1-carboxylic acid chloride ( 38
The title compound (0.39 g) was obtained as colorless needles (recrystallized from ethyl acetate-ethanol) from 2.5 mg) and 4'-(4-octylphenylcarbonyloxy)-4-biphenol (0.95 g). .

Example 5 Cis-(IR,2S)-2-methoxycyclohexane-
1-carboxylic acid 4'-(4-n-octyloxyphenyloxycarbonyl)-4-bi() +, -
Synthesis of (+) cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid The present optically active cyclic dichiral carboxylic acid can be produced by the following route. I can do it. That is, ethyl ethyl 2-oxocyclohexane-1-carboxylate was prepared using a literature method using baker's yeast [BJ, Doel et al., Au5t, J, Ch.
e-, 29, 2459 (1979)] and then the obtained cis-(IR12S)-2
-Hydroxycyclohexane-1-carboxylic acid ethyl ester was subjected to a methylation reaction, followed by an acidic hydrolysis reaction to obtain the title compound.

'H- of the ethyl ester (colorless oil) of the title compound
The NMR spectrum is shown below. t'H-NMR (9
0MIIz, CDCN 3) δ: 0.8-2.2 (8H
, m, CR2), 1. 25 (3H.

t, J-7Hz, Co2CH2Cdan3. ), 2.2\ -2-55 (IHlml CHCO2Et).

/ 3, 29 (3H1s, OCHa), 3.55-
＼ 3, 9 (I H= m, CHOCHs) , 3
．． 9/--4,35(2H,m,Co2CH2CH5)01) Esterification reaction 1,05 g of 4-octyloxyphenyl ester of 4'-hydroxy-4-biphenylcarboxylic acid and 0.6 g of pyridine in 10 m of dry tetrahydrofuran ! In the solution (
Cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid obtained in section 1)4. Acid chloride (I Rν”t) obtained by reacting Og with oxalyl chloride
cm-': 180aX OH-NMR (90MII, CDCff 3) δ: 0,
85-2.55 (8H, m, CR2).

2.6-3.05 (IH, m, CH-C-Cfl)
.

3.34 (3H1s, 0CHa), 3.8-\4, 3 (I Hlm, C-HOCHa)
2. 0.5 g of 2 g/- was added at room temperature while stirring.

After reacting overnight, the reaction solution was concentrated under reduced pressure. The residue was dissolved in silica gel and carbon tetrachloride-ether (30:
1) Separation by column chromatography using
Purification and recrystallization from ethanol gave 0.3 g of the title compound. The IR,'H-NMR spectrum of the crystal is shown below.

IRνKB'cx+-': 2800-3000.17
40゜l1ax'H-NMR (90MHz, CDCΩ3) δ: 0.
89 (3H, t), 1. 1-2.0 (2
0H, m), 2.6-2.9 (IH, m).

3.40 (3H, s), 3.9-4. 1 (3
H.

m), 6.8-8. 3 (12H, m) Example 6 cis-(IR2S)-2-methoxycyclohexane-1
-carboxylic acid 4- (4' -n-octyloxy-
4-biphenyloxycarbonyl) phenyl ester (
In formula [1']) R1 is n-CHR is CHSQ S
In the same manner as in Example 5, cis-(IR, 2S)-2-methoxycyclohexane-1-carboxylic acid chloride 0.5
The title compound was synthesized from 0.0 g and 1.05 g of 4-(4'-octyloxy-4-biphenyloxycarbonyl)phenol and crystallized from ethanol. 38j- was obtained.

Example 7 Cis-(IR,2S)-2-methoxycyclohexane-
4'-octyloxy-4-biphenyl ester of 1-carboxylic acid (in the formula [I'], R is n-C8H17,
R2 is CH3, Ql, Q3II t'---
In the same manner as in Example 5, 0.7 g of cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride and 4' The title compound (0.62 g) was obtained from 1.05 g of -octyloxy-4-biphenol.

Example 8 Cis-(IR,2S)-2-methoxycyclohexane-
4'-(4-octyloxyphenylcarbonyloxy)-4-biphenyl ester of 1-carboxylic acid (formula [
I'], R1 is nCHR is CH3, Q11Q3 is O 817ゝ 2 , cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride 0.5
0g and 4-octyloxybenzoic acid 4'-hydroxy-
From 1.05 g of 4-biphenyl ester, the title compound (0
, 77g) was obtained.

Example 9 (i) Production of trans-(Is,2S)-2-methoxycyclopentane-1-carboxylic acid Cis(1R,2S)-hydroxycyclopentane-1-carboxylic acid produced in Example 1-(+) Inverting the configuration of the 1-position of the acid ethyl ester in the presence of a base (K2CO3) in ethanol, converting it to trans-(Is, 2S)-2-hydroxybencune-1 carboxylic acid ethyl ester,
The quartz crystals were subjected to a methyl etherification reaction followed by an acidic hydrolysis reaction to obtain the title compound.

0H H (il) Esterification reaction Example 1-(if) In the same manner as in
S)-2-methoxycyclopentane-1-carboxylic acid chloride lylide trans-(IS.

The compound of Example 9 was obtained by condensation reaction of 4'-hydroxy-4-biphenylcarboxylic acid with 4-octyloxyphenyl ester using 2S)-2-methoxycyclopencune-1-carboxylic acid chloride.

Example 10.11 Example 9 - Manufactured by (i) - Kuchibuichitoranosu (IS).

2S)-2-Methoxycyclopentane-1-carboxylic acid was converted into an acid chloride form by a conventional method, and then subjected to a condensation reaction with the corresponding phenolic hydroxyl compound to obtain Example 1.
0.11 of the compound was obtained.

Example 12 Cis-(IR,2S)-2-methoxycyclohexane-
4-(4-octyloxyphenyloxycarbonyl)phenyl ester of 1-carboxylic acid (in formula [1'], R is n Cs Hr 7, R2 is CH3"!"3 is 10-1Q2 is X 10- Production of C-1 (◇→, -◇← is ÷) In the same manner as in Example 5, cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride 0.68. and 4 -(4
A surface layer compound (1.30 sr) was obtained from 1.03 g of -octyloxyphenyloxycarbonyl)phenol.

Implementation flJ13 cis-(IR,2S)-2-methoxycyclohexane-
4'-octyloxycarbonyl-4 of 1-carboxylic acid
-biphenyl ester (formula [11% formula% -2-methoxycyclohexane-1-carboxylic acid chloride 0.80 g and 4'-octyloxycarbonyl-4-
From 1.14 g of biphenol to the title compound (0.80 g)
I got it.

Example 14 Cis-(IR,2S)-2-methoxycyclohexane-
4'-(4-octylphenyloxycarbonyl)-4-biphenyl ester of 1-carboxylic acid (formula [■']
where R is n Cs Hty, R is CH3, Ql is a single bond, and Q2 is -(◇→, -O→ is ÷).

In the same manner as in Example 5, cis-(IR, 2S), Vero←, Beka← and →ri← products were produced.

In the same manner as in Example 5, cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride (0,
57 g) and 1.00 g of 4'-(4-n-octylphenyloxycarbonyl)-4-biphenol, the title compound (1,04) g was obtained.

Example 15 Cis-(IR,2S)-2-methoxycyclohexane-
4-(4'-octyloxy-4- of 1-carboxylic acid)
biphenylcarbonyloxy) phenyl ester (formula [
I'], R1 is nCHR is CH3, Ql, Q3 is -
The title compound (1.05 g) was obtained from 1.05 g of 0.0 L.

Example 16 Cis-(IR,2S)-2-methoxycyclohexane-
4'-(4-n-propyloxyphenyloxycarbonyl)-4-biphenyl ester of 1-carboxylic acid (in formula [I'], R1 is n -CH, R is CH3, Q11
Q3 is -O-X is a single bond, Y is -C-0- +, and ÷).

In the same manner as in Example 5, cis-(IR,2S)2-methoxycyclohexane-1-carboxylic acid chloride 0.57
g and 4-(4'-octyloxy-4-biphenylcarbonyloxy)pheno-X, 10-C-1Y is a single bond, and the sha and + sha are →2H).

In the same manner as in Example 5, 0.6 cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride
The title compound (1.05 g) was obtained from 1.05 g of 4'-(4-n-propyloxyphenyloxycarbonyl)-4-biphenol.

Example 17 4'-decyloxy-4-biphenyl ester of cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid (R in formula [1']).

is n-CH, R is CH3, QISQ3 is (), -(E)
← Manufacture of −(D←).

In the same manner as in Example 5, 0.6 cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride
9g and 0.98g of 4'-decyloxy-4-biphenol
The title compound (0.72 g) was obtained from the following.

Example 18 Cis-(IR,2S)-2-methoxychlorohexane-
4'-dodecyloxy-4-biphenyl ester of 1-carboxylic acid (in formula [I'], R is "12H25, R
2 is CH3, Ql, Q3 100-, building, is ÷) manufacturing.

In the same manner as in Example 5, 0.6 cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride
9g and 4'-dodecyloxy-4-biphenol 1.06
The title compound (0.4 g) was obtained from g.

Example 1 cis-(IR52S)-2-methoxycyclohexane-
4'-(4-octyloxybenzyloxy)-4-biphenyl ester of 1-carboxylic acid (formula [■'], R is n-C8H17, R2■ is CH, Q, Q is -〇-1Q2 is Manufacture.

In the same manner as in Example 5, 0.5 cis-(IR,2S)-2-methoxycyclohexane-1-carboxylic acid chloride
7. and 4'-(4-octyloxybenzyloxy)
From 1.01 g of -4-biphenol, the title compound (0,3
2g) was obtained.

Example 20 Cis-(IR,2S)-2-butoxycyclopentane-
4'-(4-n-octyloxyphenylcarbonyloxy)-4-biphenyl ester of 1-carboxylic acid (formula [1'], R1 is n-C8H17, R2 is Bu(n
), QISQ3 is 10-0X is -C-0-1Y is a single bond, sha, sha → X is manufactured.

(i) Synthesis of cis-(IR,2S)-2-butoxycyclopentane-1-carboxylic acid The present optically active cyclic dichiral carboxylic acid can be produced by the following route.

÷) cis-(IR,2S)-2 obtained in Example 1-(i)
-Hroxycyclopenkune-1-carboxylic acid ethyl ester was subjected to a butylation reaction and then subjected to an acidic hydrolysis reaction to produce the title compound.

The 'H-NMR vector of the title compound is shown below.

'HNMR (90Ml1z, CDCl2a) δ: 0
．． 7-1.05 (3H, m, CHs) jl,
05-2, 5 (10H, m, CH2), 1.26
(3H, t, J-7, 1511z, OCR2C Dan 3).

2-6 3-0 (lHlm, CHC02E t )
.

/ 3.1-3.6 (2H, m, 0CH2CH2-).

3.85-4.3 (LH, m,, CHOBu).

4, 14 (2H, q, J-7, 15Hz.

-c-ocdan2CH3) (11) Esterification reaction 4'-(4-n-octyloxyphenylcarbonyloxy)-4-biphenol ester 0.71 g and pyridine 0.4 g in 10 ml of dry tetrahydrofuran solution, (1) Add 0.35 g of acid chloride obtained by reacting oxalyl chloride to 1.0 g of cis-(IR,2S)-2-butoxycyclopentane-1-carboxylic acid obtained in Section 1), and add while stirring at room temperature. Ta.

After reacting overnight, the reaction solution was concentrated under reduced pressure.

Silica gel and carbon tetrachloride-ether (30
: Separation and purification by column chromatography using 1) and recrystallization from ethanol gave 0.63 g of the title compound.

Example 21 Cis-(IR,2S)-2-butoxycyclopenkune-
4-(4'-octyloxy-4- of 1-carboxylic acid)
Biphenyloxycarbonylphenyl ester (formula [I
'], R, is n -C8H17, R2 is n B
us QI SQ3 is 10-X is a single bond, Y is 10-C
- Manufacture of buildings, buildings, and buildings (where ← is ÷).

In the same manner as in Example 1, 0.3 cis-(IR,2S)-2-butoxycyclopentane-1-carboxylic acid chloride
The title compound (0.78 g) was obtained from 5 g and 0.71 st of 4-(4'-octyloxy-4-biphenyloxycarbonyl)phenol.

Example 22 Cis-(IR,2S)-2-methoxy-1-methylcyclopentanecarboxylic acid Cis-(IR,2S)-2 prepared in Example 1-(i)
-Hydroxycyclopencune carboxylic acid ethyl ester as described by Prater et al. [Tetrahedron, 40.
1269 (1984)] and Morl and Ebata [T
et rahed ron.

42.4413 (1986)], methylation, methyl etherification, and subsequent hydrolysis reaction were performed to obtain the title compound as a colorless oil (formula below).

O The IR spectrum of the crystal is shown below.

I R, nea-'': 1700-2300゜a+a
X (if) Esterification reaction Example 22 The compound was obtained in the same manner as in Example 1-(II).

Examples 23, 24 and 25 shown in Table 1 Example 22 - Cis-(IR,2S)-2 obtained in (+)
-Methoxy-1-methylcyclopentanecarboxylic acid was subjected to a condensation reaction with an appropriate skeleton compound according to the method described above, for example, the method of Example 1-(11), to obtain the compounds shown in Table 1.

Example 26 Preparation of 4'-octyloxy-4-biphenyl ester of 4-(trans-(IR,2S)-2-methoxymethyl-1-cyclopentyloxy)benzoic acid.

Synthesis of (+)cis(Is,2S)-2-methoxymethyl-cyclopentanol The present optically active cyclic dichiral alcohol can be produced by the following route. That is, the cis-(
IR,2S)-2-hydroxycyclopencunecarboxylic acid ethyl ester is tetrahydropyranylated, reduced with lithium aluminum hydride, then subjected to a methylation reaction, and further detetrahydropyranylated with an ion exchange resin to obtain the title compound. I got it. IR and 'H-NMR of this product
The spectrum is shown below.

IRν"tam-': 3200-3700.28001
aX-3000,1740 LH-NMR (90MHz, CDCf1a) δ
: 1.4-1.9 (6H, m), 2.3-2.5 (I
H, broad), 3.36 (s, 3H).

3.52 (IH, s), 3.6 (IH, s).

4.2-4.4 (m, 2H) (11) Etherification reaction 0.49 g of optically active alcohol, 4'-octyloxy-4-biphenyl ester of 4-hydroxybenzoic acid 1. o5 g,) 0.98 g of liphenylphosphine is dissolved in 10 ml of dry tetrahydrofuran, then 0.65 g of diethyl azodicarboxylate is dissolved in 10 ml of dry tetrahydrofuran. was added while stirring at room temperature. After stirring the reaction solution at room temperature for 1 hour, the solvent was distilled off.

The residue was dissolved in silica gel and carbon tetrachloride-ether (30
: Column chromatography using 1) gave the example compound (0.60 g).

The IR,'H-NMR spectrum of this product is shown below.

IRI/n8"c+n-':800-3000.173
'5゜fiax IH-NMR (90MIIz, CDCNa) δ
:0.9 (t, 3H), 1.2-1.5 (
m, 12H), 1.6-2.0 (m, 6H),
2.2-2. 5 (m, IH), 3. 34
(t, 5H).

4.0 (d, 2H), 4.6-4.8 (m,
IH), 6. 9-8. 2 (m, 12H)
Example 27 4'-octyloxy-4-biphenylcarboxylic acid
-(trans-(IR,2S)-2-methoxymethyl-
Production of 1-cyclopentyloxy)phenyl ester In the same manner as in Example 26, cis-(Is,2S)-2-
Methoxymethyl-cyclopentanol 0.49g and 4'
The title compound (0.70 g) was obtained from 1.05 g of 4-hydroxyphenyl ester of -octyloxy-4-biphenylcarboxylic acid.

Example 28 4'-() lance-( of 4-octyloxybenzoic acid
Production of IR,2S)-2-methoxymethyl-1-cyclopentyloxy)-4-biphenyl ester In the same manner as in Example 26, cis-(Is,2S)-2-
Methoxymethyl-cyclopentanol 0.49t and 4-
The title compound (0.61 st) was obtained from 1.05 g of 4'-hydroxyphenyl ester of octyloxybenzoic acid.

Example 29 Preparation of 4-octyloxyphenyl ester of 4'-(trans-(IR,2S)-2-methoxymethyl-1-cyclopentyloxy)-4-biphenylcarboxylic acid In the same manner as in Example 26, cis- (Is, 2S)-2-
Methoxymethyl-cyclopentanol 0.49g and 4'
4-octyloxyphenyl ester of -hydroxybiphenyl-4-carboxylic acid 1,05. from the title compound (
0.76 g) was obtained.

Example 30 Preparation of trans-(IR,2S)-2-methoxymethyl-1-cyclopentyl ester of 4'-octyloxy-4-biphenylcarboxylic acid In the same manner as in Example 26,
0.59 g of cis-(1s,2S)-2-methoxymethyl-1-cyclopentanol and 4'-octyloxy-4
-Biphenylcarboxylic acid to title compound (0,35g)
I got it.

Example 31 trans-(IR,2S)-2-methoxymethyl-1-
Production of 4'-octyloxy-4-biphenyl ether of cyclopentanol In the same manner as in Example 26, cis-(Is,2S)-2-
Methoxymethyl-1-cyclopentanol 0.68. The title compound (0.78 g) was obtained from and 4'-octyloxy-4-biphenol.

Example 32 Cis-(Is, 2S)-2- of 4-(4'-octyloxy-4-biphenyloxycarbonyl)benzoic acid
Preparation of methoxymethyl-1-cyclopentyl ester (i) Esterification 1.11 g of 4-(4'-octyloxy-4-biphenyloxycarbonyl)benzoic acid and 20 m of thionyl chloride
After adding 1 and heating under reflux for 3 hours, the reaction solution was concentrated under reduced pressure. 20 ml of thionyl chloride was added to the residue, and the mixture was heated under reflux for 4 hours. The reaction solution was concentrated under reduced pressure, toluene was added to the residue, and excess thionyl chloride was azeotropically distilled off. 25 ml of dry tetrahydrofuran was added to the residue to dissolve it, and cis-(
0.39 g of Is, 2S)-2-methoxymethyl-cyclopentanol and 0.40 g of pyridine were added, and the mixture was stirred at room temperature overnight. The reaction solution was concentrated under reduced pressure, and the residue was subjected to column chromatography using silica gel and carbon tetrachloride-ether (30:1) to obtain the title compound (0,10
g) was obtained.

Example 33 In the same manner as in Example 32, the example compounds shown in Table 1 were obtained.

Example 34, 35.36, 37.38, 39°40.4
1,42.43.44 and 45 In the same manner as in Example 1, the examples shown in Table 1 were prepared by condensation reaction of cis-(IR,2S)-2-methoxycyclopentanecarboxylic acid chloride with a suitable skeleton compound. An example compound was obtained.

Example 46 (+)cis-(Is,2S)-1-hydroxymethyl-
Synthesis of 2-Methoxycyclopentane Example 1 - The compound described in section (+), cis-(JR,2S)-2-hydroxycyclopentanecarboxylic acid ethyl ester, was converted into lithium alumina hydride (L L Afl H4) 3 , 4
K. ether (500 ml) was added to the suspension at 0° C. with stirring.

After stirring at 0°C for 1 hour, add 4.6 mL of cold water to the reaction solution.
4.6 ml of 15% NaOH aqueous solution, then 14 ml of cold water
1 was added carefully one after another at 0°C with stirring. Insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and the residue was subjected to vacuum distillation to obtain the title compound as a colorless oil (formula below). Collection ff112. Or.

Bp61-64℃ (4mm) Ig) 'HNMR (90MHz, CDCDa) 62g
-5,711z, OH), 3. 31 (3H
,s.

OCH3), 3.4-4.0 (3H, m.

(II) Condensation Reaction Example 26 - The compound of Example 46 shown in Table 1 was obtained by the same method as described in section (li).

Example 47 Preparation of 4'-octyloxy-4-biphenyl ester of cis-(IR,2S)-2-methoxycarbonylcyclohex-4-enecarboxylic acid Literature method [M, 0h
No et al., Tetrahedron Lett, 24
．． 2557. (1984)] synthesized by cis-
To 0.25 g of (IR,2S)-2-methoxycarbonylcyclohex-4-enecarboxylic acid was added 3 ml of oxalyl chloride under water cooling, and the mixture was stirred for 2 hours. Excess oxalyl chloride was distilled off, and 5 ml of dry tetrahydrofuran and 0.30 g of 4'-octyloxy-4-biphenol were added to the remaining crude acid chloride, and 0.11 g of triethylamine was added dropwise under water cooling. After stirring for 1 hour, the reaction solution was concentrated under reduced pressure, and carbon tetrachloride was added to the residue. Insoluble materials were removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was mixed with silica gel and carbon tetrachloride-ethyl acetate (20:1
) and then recrystallized from ethanol to obtain the title compound (0,3
1 g) was obtained as a colorless flake-like product. The IR and 'H-NMR spectra of the main island are shown below.

0.89 (3H, t, -CH2C dan,).

1.12 2.00 (12H, m, CH2>.

2, 18-2.95 (4H, m, Cdan2-C-c-
cdan2), 3.10-3.42 <2H, m.

-0OC-CH-CH-Coo-), 3.72 (3H,
s, 0CHa), 3.98 (2H, t.

J = 6Hz, OCH2), 5.73 (2H
, m.

CH-CM), 6.85-7.60 (8H, m.

Aromatic H) Example 48 Preparation of 4'(4-octyloxyphenyloxycarbonyl)-4-biphenyl ester of cis-(IR,2S)-2-methoxycarbonylcyclohex-4-enecarboxylic acid Example 47 and Similarly, cis-(IR,2S)-2-
Methoxycarbonylcyclohex-4-enecarboxylic acid 0.22. and 4'-(4-octyloxyphenyloxycarbonyl)-4-biphenol 0.50. from the title compound 0.42. I got it.

Example 49 Production of 4'-(4-octyloxyphenyloxycarbonyl)-4-biphenyl ester of cis-(IR,2S)-2-methoxycarbonylcyclohexanecarboxylic acid Cis-(IR,2S) obtained in Example 48 )-2-methoxycarbonylcyclohex-4-enecarboxylic acid 4'
-(4-octyloxyphenyloxycarbonyl)-
0.20° of 4-biphenol was dissolved in 10 ml of chloroform, 30 mg of 5% palladium on carbon was added, and hydrogenation was carried out at room temperature under normal pressure. After the reaction was completed, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 0.18 g of the title compound. The IR and 'H-NMR spectra of the crystal are shown below.

0.89 (3H, t, -CH2Cdan3).

1, 15 2.47 (20H, m, CH2).

2.93-3.20 (2H, m, 0OC-CH-C
H-Coo-), 3.72 (3H,s.

0CHa) -3,96 (2H, t, J = 6Hz.

OCH2), 6.82 g, 30 (12H, m
.

Aromatic H) Example 50 Preparation of 4'-octyloxy-4-biphenyl ester of cis-(IR,2S)-2-methoxycarbonylcyclohexanecarboxylic acid Cis-(IR,2S)-2 obtained in Example 47 -4'- of methoxycarbonylcyclohex-4-enecarboxylic acid
0.15 g of the title compound was obtained from 0.18 g of octyloxy-4-biphenyl ester in the same manner as in Example 49.

Example 51 Preparation of cis-(3R,4S)-tetrahydro-3-methoxycarbonyl-4-thienyl ester of 4-(4'-octyloxy-4-biphenolicyloxy)benzoic acid (i) Cis-( Synthesis of 3R,4S)-tetrahydro-4-trimethylsilyloxythiophene-3-carboxylic acid methyl ester The present optically active cyclic dichiral compound can be produced by the following route.

That is, tetrahydro-4-oxothiophene-3-
A literature method using baker's yeast to prepare carboxylic acid methyl ester [R, W, II of Tmann et al., Tetrahed
ronLett, 23.3479 (1982)], and the resulting cis-(3R,4S)
-Tetrahydro-4-hydroxythiophene-3-carboxylic acid methyl ester is trimethylsilylated by a conventional method using 1,1,1,3゜3.3-hexamethyldisilazane to trimethylsilylate it according to the title. The title compound was thus obtained. The IR and 'H-NMR spectra of this product are shown below.

0.11 (9H, s, -St (CH3)5).

2, 70-3.40 (5H, m.

-Ctan2SCdan2Cdan-Co2-), 3.70(3
H,s, OCHa), 4.83 (IH,m
.

>CH-os 1) (il) Esterification reaction 0.50 g of 4-(4'-octyloxy-4-biphenylcarbonyloxy)benzoic acid and 10 m of thionyl chloride
1 was added thereto, and the mixture was heated under reflux for 4 hours. Excess thionyl chloride was distilled off, and 20 ml of dry acetonitrile was added to the remaining crude acid chloride. 15a+g of zinc chloride and 0626 g of cis-(3R,4S)-tetrahydro-4-trimethylsilyloxythiophene-3-carboxylic acid methyl ester obtained in section (1) were added, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the reaction solution was concentrated, separated and purified by column chromatography using silica gel and dichloromethane-ethyl acetate (10:1), and then recrystallized from dichloromethane-methanol (1:10) to obtain the title compound. Compound (0,3
6 g) was obtained as colorless powder crystals. IR1'H- of this product
The NMR spectrum is shown below.

'HNMR (90H) Iz, CD Ci) a)
δ: 0.90 (3H, t, -CH2C dan,).

1, 10-2. OO(12H, m, CH2).

3, 03-3. 56 (5H, m.

-CH,SCH,,CH-Co2-), 3.68(3H
,s,0CHa),4.02(2H,t.

J = 6Hz, 0CR2), 5.97 (IH,
m.

>CH-OS i), 6.88-8. 30 (12
H, m, aromatic H) Example 52 Preparation of cis-(3R,4S)-tetrahydro-3-methoxycarbonyl-4-thienyl ester of 4'-octyloxy-4-biphenylcarboxylic acid Proceed as in Example 51. , cis-(3R,4S)-tetrahydro-4-trimethylsilyloxythiophene-3
The title compound (0.42 g) was obtained as colorless powder crystals [recrystallized from dichloromethane-methanol (1:10)] from 0.36 g of -carboxylic acid methyl ester and 0.50 g of 4'-octyloxy-4-biphenylcarboxylic acid. Ta.

Example 53 Preparation of cis-(3R,4S)-tetrahydro-3-methoxycarbonyl-4-thienyl ester of 4-(4'-octyloxy-4-biphenyloxycarbonyl)benzoic acid In the same manner as in Example 51, cis-(3R,4S)-tetrahydro-4-trimethylsilyloxythiophene-3
-0.26 g of carboxylic acid methyl ester and 4-(4
From 0.50 r of -octyloxy-4biphenyloxycarbonyl)benzoic acid, the title compound (0.14 g) was converted into colorless powder crystals [dichloromethane-methanol (1:10
) was obtained as a recrystallized product.

Example 54 Preparation of cis-(2R,3S)-tetrahydro-2-methoxycarbonyl-3-thienyl ester of 4-(4′-octyloxy-4-biphenylcarbonyloxy)benzoic acid (i) Cis-(2R, Synthesis of 3S)-tetrahydro-3-trimethylsilyloxythiophene-2-carboxylic acid methyl ester The present optically active cyclic dichiral compound can be produced by the following route.

Me SiOCo2Me i.e. tetrahydro-3-oxothiophene-2-
A literature method using baker's yeast to prepare carboxylic acid methyl ester [R,W, Hoffmann et al., Tetrahed
ronLeti, 23.3479 (1982)], and the resulting cis-(2R,3S)
-Tetrahydro-3-hydroxythiophene-2-carboxylic acid methyl ester was trimethylsilylated using 1,1,1.3°3.3-hexamethyldisilazane in a conventional manner to obtain the title compound. Favorite IR
and 'H-NMR spectra are shown below.

'H-NMR (90MHz, C, D Cfla
) δ;0, 12 (9H,s, -S i (CH3
) 3).

2,78-3.30 (4H,m, -Cdan2CH2-
S), 3.72 (3H,s.

-0CR), 3.89 (IH, d, -δH-S).

□3 □4.80
(IH, m, > CH-O81) (ll) Esterification reaction 0.70 g of 4-(4'-octyloxy-4-biphenylcarbonyloxy)benzoic acid and 10 m of thionyl chloride
1 was added thereto, and the mixture was heated under reflux for 4 hours. Excess thionyl chloride was distilled off, and the remaining crude acid chloride was mixed with 15 ml of dry acetonitrile, 27 w+g of zinc chloride, and cis-(2R,3S)-tetrahydro-3-trimethylsilylthiophene-2-carboxylic acid obtained in section (i). acid methyl ester 0
．． 40 r was added, and the mixture was heated under reflux for 1 hour. After the reaction was completed, the reaction solution was concentrated, separated and purified by column chromatography using silica gel and n-hexane-ethyl acetate (10:1), and then recrystallized from ethanol to obtain the title compound (0:1). , 154r) was obtained as a colorless powder. The desired 'H-NMR spectrum is shown below.

'H-NMR (90MIIz, CDCf13) δ:
0.90 (3H, t, -CH2 then 3).

1.15-1.60 (IOH,b, -Cdan2-).

1.60-1.98 (2H, m.

-0CH2■2CH2-), 2.21-2, 87 (
2H9m, OCH-CH2-CH2), 2.91 3
．． 40 (2H, m.

-CH2-9dan2-5-), 3.60 (3H.

s, OCHa), 4.02 (2H1t.

-O, CH2-), 4.32 (IH, d.

>CH-S-), 5.78 (IH, d, t
.

>CM-0-), 6.94-8.26 (12H.

m, aromatic H) Example 55 Preparation of 4'-octyloxy-4-biphenyl ester of cis-(3R,4S)-tetrahydro-4-methoxyfuran-3-carboxylic acid (1) Cis-(3R,4S )−
Synthesis of tetrahydro-4-methoxyfuran-3-carboxylic acid ethyl ester The present optically active cyclic dichiral carboxylic acid ethyl ester can be produced by the following route. That is, 4-oxotetrahydrofuran-3-carboxylic acid ethyl ester is subjected to asymmetric reduction using baker's yeast, and then the obtained cis-(3R,4S)-
4-Hydroxytetrahydrofuran-3-carboxylic acid ethyl ester was subjected to a methylation reaction to obtain the title compound.

The IR and 'H-NMR spectra of the favorite are shown below.

'HNMR(90Mtlz, CDCDa)δ
:1.30 (3H, t, -0CH2■3).

3, 30 (3H,s, -OCHa), 3.43
3-57 (I Hlm, HC-C02E t)
.

number 4, 17 (2H, q, -QCdan 2CH3).

3, 70-4.45 (5H, m.

HC-OCH-CH-0-CH2-) -13″ 2 (it) Cis-(3R,4S)-tetrahydro-4 obtained by esterification reaction (+)
-methoxyfuran-3-carboxylic acid ethyl ester 20
0 mg was added to a mixture of 2 ml of dioxane and 2 ml of 2N hydrochloric acid, and the mixture was stirred at 80° C. for 5 hours and subjected to acid hydrolysis. The obtained crude carboxylic acid oxalyl chloride was allowed to act, and acid chloride compound 2 was added. - After stirring at night, the reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: chloroform) to obtain the present example compound 190.
mg was obtained. The IR1'H-NMR spectrum of this product is shown.

'HNMR (90M1lz, CDCIlg)
δ: 0.90 (3H, t, -CH2C dan,).

1-10-2.00 (12H, m, CH2-)3,
33-3. 60 (LH, m.

10CH3'), 3.83-4.47 (5H.

-CHOCH-, -CH-0CH3).

4,00 (2H,t, -CH20(0)6,85-7
．． 60 (8H, m, aromatic H)4-octyloxy-
A solution of 596 II g of 4-biphenol and 202 g of triethylamine in dry tetrahydrofuran (10 ml) was stirred at room temperature.

6.80-7.60 (8H, m.

In the same manner as in Example 1, cis-(IR,2S)-2-methoxycyclobencune-1-carboxylic acid chloride (0,
The compound of this example (0.70 g) was obtained as an oily substance from the skeleton compound 4'-(7-octenyl)oxy-4-biphenol (0.93 g). 1H-N of this product
The MR spectrum data is shown below.

IH-NMR (CD(1!3)δ:1.35-2,4
0 (14H, m, CH2), 3. 10H,s,
OCH3), 3.98 (2H, t.

J=611z, OCH2), 4. 10 (IH
Tai J-8゜511z, CH2-C\) 5゜01 Example 57 In the same manner as in Example 1, cis-(IR,2S)-2-methoxycyclopentane-1-carboxylic acid chloride (0,
50g) and the skeleton compound 4-(2-octylthio-5-
From pyrimidinylphenol (0.88 g), the compound of this example (0.76 g) was prepared in the form of colorless phosphorus flakes (ethyl acetate).
Recrystallized from hexane). 'H-NMR of this product
The spectral data is shown below.

'H-NMR (CDIJ) 3) δ: 0.88 (3
Ht, -CH2-Cdan3), 1.12-2.40 (18
H, m, CH2), 3°J = 7 Hz, S-CH2), 3°H,m
, CH-Coo), 3゜0CH3), 4.14
(IH.

0CR3), 7.21 (2H.

Aromatic H), 7. 52 (2H.

Aromatic H), 8.69 (2H.

Example 58 19 (2H, t.

0-3. 2 (1 39 (3H, s.

m, CH- d, J=911z.

d, J=9Hz.

S, aromatic H) The following is shown.

'H-NMR (CDCl2) δ: 1.60-2°30
(12H, m, CH2) , 2.35 (IH, m
, HCC-), 3.10 (IH.

0CHa) = 4.00 (2H,t, J-6
11z.

-○-CH2-), 4.10 (IH, m.

*(H-OCH3), 6.88-7.52 (8 Example 1
In the same manner as above, cis-(IR,2S)-2-methoxycyclopencune-1-carboxylic acid chloride (0.53 g)
and, the present example compound (0,9
2 g) was obtained as colorless scales (recrystallized from hot EtOH). Example 59 The 'H-NMR spectrum data of this product was analyzed in the same manner as in Example 1.
0g) and 4'-(2-hebutenyl)-4-biphenol (0.87g), the present example compound (0.64g)
was obtained as colorless needles (recrystallized from ethanol). The 'H-NMR spectrum data of this product is shown below.

'H-NMR (CDCN 3.90MHz) δ: 0,
7-1-05 (3Hlm, CHa).

1,05 2.5 (12H, m, CH2).

/ 2.9-3.35 (IH, m, -0CHJ.

3, 39 (3H,s=OCH3) -4,0-4,
26 (IH, m, -0-C-CHgu).

4.50 (2H, d, g=4.7Hz, allyl CH2
), 5. 5-6.1 (2Hlm6 Vinyl H)
, 6.8-7.65 (8H, m, aromatic H) Example 60 From loride (0.50 g) and 4'-(2-oftenoyloxy)-4-biphenol (0.96 g), this The example compound (0.92 g) was obtained as colorless needles (recrystallized from ethanol). The 'H-NMR spectrum data of this product is shown below.

1■-NMR (CD C1g, 90MIIz) δ:
0, 75 1.05 (3Hlm, CIs)
.

1.05-2.45 (14H, m, CH2).

2.95-3.45 (IH, m, -0CR').

\3.40 (3H,s,0CRs), 3.9-4.
3 (IH, m, -0-CCH).

6.03 (IH, d, g = 15.5 Hz, vinyl H), 6.8-7.7 (9B, m, aromatic H or vinyl H) In the same manner as in Example 1, cis (IR, 2S )-2-Methoxycyclopenkune-1-carboxylic acid Application Example 1 The optically active compound of the present invention shown in the above example was added to the conventionally known ferroelectric liquid crystal compound shown in Table 2 (hereinafter referred to as base liquid crystal). A liquid crystal composition containing the optically active compound of the present invention was obtained by quantitative blending.

The spontaneous polarization of this invention and the base liquid crystal alone were measured, and the results are shown in Table 3.

The spontaneous polarization values in Table 3 are the values at a temperature 10° C. lower than the upper limit temperature of the chiral smectic C phase.

Table 3 Elements containing only host liquid crystals B and C did not exhibit a clear optical response. On the other hand, optical contrast was observed in the element encapsulating the composition containing the optically active compound of the present application, and the response was also extremely good.

Application Example 2 The optically active compounds of the present invention shown in Table 4 were blended into base liquid crystal A, and the spontaneous polarization was measured. The results are also listed in Table 4,
The value of spontaneous polarization is the value at a temperature 10° C. lower than the upper limit temperature of the Sc' phase.

Table 4 Base Optically active compound of the present invention (1) Spontaneous polarization value
Polyethylene terephthalate film (thickness 6w++*
) as a spacer, and a cell made of glass with transparent electrodes spin-coded and rubbed with polyimide.
A liquid crystal element was produced by encapsulating the composition shown in . A rectangular wave of 40 V p-p was applied to this at room temperature, and when observed with a polarizing microscope, the result was A 51 10
15A 51 20
28A 51 30
41A 52 10 13
A 47 30 44A
48 20 25A
--<1 Base liquid crystal A: Furthermore, the composition shown in Table 4 was applied to a cell prepared using a polyethylene terephthalate film with a thickness of 6 μm as a spacer and glass with transparent electrodes that had been spin-coated with polyimide and subjected to rubbing treatment. The liquid crystal display element shown in FIG. 1 was manufactured by encapsulating the liquid crystal shown in the uppermost row. When a 10 Hz rectangular wave of 40 V was applied to this element at room temperature and -p was observed under a polarizing microscope, an optical response could be observed. On the other hand, the sample in which the base liquid crystal shown in the bottom row of Table 4 was sealed did not exhibit an optical response of -p even when a higher voltage of 50 V was applied.

[Effects of the Invention] As is clear from the Examples and Application Examples, the present invention provides a liquid crystal compound or a liquid crystal composition that has a large spontaneous polarization and exhibits a chiral smectic C phase. Also,
By using these as ingredients in liquid crystal compositions,
This is effective in expanding the spontaneous polarization of the composition by as much as 111 times. Therefore, the optically active compound of the present invention and the liquid crystal composition containing the same are useful as liquid crystals used in light modulation devices such as liquid crystal display devices, and provide devices with excellent performance such as responsiveness.

[Brief explanation of drawings]

FIG. 1 shows an example of a liquid crystal display element according to the present invention. 1 and 8 are polarizing plates, 2 is a front glass, 3 and 6 are transparent electrodes, 4 is a ferroelectric liquid crystal phase, 5 is a seal, and 7 is a rear glass, respectively. Agent Akira Asamura Procedural Amendment (Voluntary) 1o Page 60 of the Specification, Line 5, F General Formula (■)” has been corrected to “General Formula (III month)”. Patent Application No. 344835 2, Title of Invention: Optically active compound, liquid crystal composition containing said compound, and liquid crystal light modulation device using said liquid crystal composition 3, Relationship with person making amendment case Name of patent applicant: Takeda Yakuhin Kogyo Co., Ltd. (1 other person) 4. Agent address: 331 Shin-Otemachi Building, 2-2-1 Otemachi, Chiyoda-ku, Tokyo 100 5. Detailed explanation of the invention in the specification subject to amendment 6. Details of the amendment are as shown in the attached sheet.

Claims (10)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is an alkyl group, alkenyl group, or alkynyl group with 3 to 14 carbon atoms, and R_2 is an alkyl group with 1 to 10 carbon atoms, carbon number Indicates an alkenyl group or alkynyl group of 2 to 10, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ indicates a 5 to 8 membered ring that may contain a hetero atom other than carbon or a double bond, and Q_1 is a single bond , (thio)ether bond, carboxylic acid ester bond,
Indicates carbonyl bond, carbonyl dioxy bond, Q_
2 and Q_3 each represent a single bond, (thio)ether bond, carboxylic acid ester bond, carbonyl bond, carbonyldioxy bond, or methyleneoxy bond, and M
▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼
Indicates a methyleneoxy bond or an ethylene bond, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Each has 1 or 2 ring constituent atoms. 6-membered ring-1,4-diyl group which may have 6 oxygen atoms or nitrogen atoms)
shows. Further, carbons marked with * mean asymmetric carbons. ] An optically active compound represented by. (2) In claim 1, the two polar groups bonded to the asymmetric carbon atoms of the 5- to 8-membered ring represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc., form a conformation in the same direction. optically active compound. (3) An optically active compound according to claim 1, in which asymmetric carbon atoms are adjacent to each other, and the mutual positions of Q_2 and Q_3 bonded to the asymmetric carbon atoms are in the cis configuration. (4) The optically active compound according to claim 1, wherein R_1 is an alkyl group having 6 to 11 carbon atoms, and R_2 is an alkyl group having 1 to 8 carbon atoms. (5) In claim 1, Q_1 is a single bond, (thio)
An optically active compound in which Q_2 is a forward or reverse ester or ether bond, and Q_3 is a (thio)ether bond, a forward or reverse ester bond. (6) In Claim 1, M is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X or one of them is a single bond and the other is a carboxylic acid ester bond, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ are both P-phenylene or at least one is 2
, 5-pyrimidinediyl. (7) In claim 1, M is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X is a single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are both P- An optically active compound in which phenylene or either one is 2,5-pyrimidinediyl. (8) Formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2 is an alkyl group with 1 to 10 carbon atoms, 2 carbon atoms
~10 alkenyl groups or alkynyl groups, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ indicates a 5- to 8-membered ring that may contain a hetero atom other than carbon or a double bond, Q_3 is a single bond, ( thio)ether bond, carboxylic acid ester bond, carbonyl bond, methyleneoxy bond, Z is a hydroxyl group or COOZ' (however, Z' is hydrogen or a carbon number of 2 to 1
0 alkyl group). Further, the carbon marked with * means an asymmetric carbon. ] An optically active compound represented by. (9) A liquid crystal composition containing at least one optically active compound according to any one of claims 1 to 7 and optionally a host liquid crystal. (10) A liquid crystal light modulator comprising the liquid crystal composition according to claim 9 disposed between at least a pair of substrates.