JPH0320235A - 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 or alkenyl; R2 and R3 are 1-3C alkyl: R4 is 1-10C alkyl; Q1 to Q3 are single bond, (thio)ether bond, (thio)carboxylic acid ester bond, carbonyl bond or carbonyldioxy bond; (n) is integer of 2-6; M is group of formula II or formula III (X and Y are single bond, (thio)carboxylic acid ester bond, methyleneoxy bond or ethylene bond; the rings A, B and C are homocyclic or heterocyclic 6-membered ring which may contain O or N); asterisk represents asymmetric carbon atom]. EXAMPLE:4'-[(1R,4S)-1-methyl-4-methoxypentyloxy]4-biphenylcarboxylic acid 4-octyloxyphenyl ester. USE:A liquid crystal compound. PREPARATION:A compound of formula I wherein Q2 is CO-O can be produced by condensing a compound of formula N with a compound of formula V in an organic solvent in the presence of a protonic acid (e.g. sulfuric acid).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an optically active compound and a liquid crystal composition containing the compound. The compound of the present invention and the composite bottom containing the same exhibit a ferroelectric liquid crystal phase, and are useful as electro-optical switching elements such as liquid crystal display elements, and can be applied to liquid crystal light modulation devices.

[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, a liquid crystal display device using a nematic liquid crystal called a twisted nematic type (TN type) is used. However, the display device using this nematic liquid product has a drawback that the response is very slow compared to other light-emitting display devices such as CRT and EL. Therefore, when applied to large-screen displays that display a large amount of information, it is not possible to display images with good contrast, which has been a constraint for wide-ranging applications. Recently, super twisted nematic (STN type) or S
A nematic liquid crystal display device with improved contrast, called BE, has been discovered. However, it is difficult to say that the response of the STN liquid crystal display has been significantly improved, and there is a need for application to displays that display a larger amount of information.

For this reason, various attempts have been made to develop new liquid product display systems with excellent responsiveness.

Since ferroelectric liquid crystals exhibit memory functions and high-speed response, there are great expectations for their application to large-screen displays. Liquid crystals exhibiting ferroelectricity are known to include chiral smectic C phase, chiral smectic H, and J phases, and among these, ferroelectric liquid crystal exhibiting chiral smectic C phase is considered to be particularly practical. It is being

The ferroelectric liquid product exhibiting chiral smectic C phase is 19
It was first synthesized in 1975 by R.B. Mayer et al., and a representative example is 4-(4'n-decyloxybenzylideneamino)cinnamic acid 1-2-methylbutyl ester (hereinafter abbreviated as DOBAMBC) [ Journal de Physique, 36, L-69 (1975
)].

A thin film type liquid crystal cell was created using DOBAMBC, and high-speed response on the μSee order was found [N, A
, Clark et al., Abrid Physics Letters, 36, 89, (1980)], we developed a liquid crystal using a ferroelectric liquid crystal exhibiting a chiral smectic C phase (hereinafter sometimes simply referred to as ferroelectric liquid crystal). Development of light modulation elements such as display elements and optical printer heads has begun.

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.

In order to put a ferroelectric liquid crystal into practical use as a liquid crystal display element, it is necessary that it has good high-speed response, orientation, memory properties, threshold properties, and the temperature dependence of these properties. Furthermore, it is necessary that the temperature range in which the chiral smectic C phase is exhibited is wide so that it can operate in a sufficiently wide temperature range including room temperature, and that it has excellent physicochemical stability.

Among these, in particular, it must be silicochemically stable, have a large spontaneous polarization to achieve high-speed response and memory properties, and have a large pitch of the helical structure to obtain good orientation. It is important that the temperature range in which the chiral smectic C phase is exhibited is wide.

However, among the ferroelectric liquid crystals developed so far, no compound has been found that can satisfy almost all of the above-mentioned properties at the same time. For example, since DOBAMBC mentioned above is a Schiff base-based liquid crystal, it has problems in terms of chemical stability against water, light, etc., and also has a small spontaneous polarization of 40 C/clI2 or less.

Ester-based liquid crystals have been reported as chemically stable ferroelectric liquid crystal compounds. However, these cannot be said to be satisfactory because the spontaneous polarization is not sufficiently large and the temperature range of the chiral smectic C phase is not sufficiently wide.

On the other hand, in order to increase the spontaneous polarization, 2 chiral carbon atoms were added as optically active groups essential for the appearance of the chiral smectic C phase.
A unique compound has been synthesized.

For example, liquid crystal compounds with dichiral epoxide side chains [
Wahlbe et al., Journal of the American Chemical Society, 108. 7424 (19
86)] or a liquid crystal compound having a halogen atom and a methyl group on the adjacent asymmetric carbon (JP-A-111-160-1)
68780, 60-218358, 61-6844
9, 62-40, 62-46, 62-10304
3, No. 62-111950, No. 62-142131, No. 62-175443, etc.).

A representative example thereof is (s)-3-methyl-2-chlorobutyl-4-(4'-octyloxyalpoxy)monobiphenylcarboxylic acid ester (Japanese Patent Application Laid-Open No. 61-68449).
There is. This liquid crystal compound has a spontaneous polarization of 180 nC
/cm2, which is a very large value.

However, since it is an aliphatic chlorine compound, it has poor chemical stability. Therefore, 4'-octyloxyluponyloxy-
4-[(s)-2-methoxy-(s)-3-methylbentyloxycarbonyl]biphenyl (JP-A-62-22
8036) are synthesized. Although this material has excellent chemical stability, its spontaneous polarization is 17 nC/cm2, which is not sufficient.

[Problems to be solved by the invention] As mentioned above, in the conventional technology, there are still various problems such as being physically and chemically stable and having large spontaneous polarization in order to achieve high-speed response and memory performance. No material has been found that can satisfy the performance.

The objects of the present invention are to have a structure that is physicochemically stable, has a large spontaneous polarization in order to realize high-speed response and memory performance, and has a large pitch of the helical structure to obtain good conformation. The object of the present invention is to provide a liquid crystal compound that satisfies important performance characteristics for practical use of ferroelectric liquid crystals in liquid crystal display devices, such as a wide temperature range in which the smectic C phase is exhibited.

[Means for Solving the Problem] In order to achieve the above object, the present inventors have developed a temperature range and a chemical structure of liquid crystal molecules exhibiting physicochemical stability, spontaneous polarization, helical pitch, and chiral smectic C phase. The present invention was achieved by conducting various studies to find a ferroelectric liquid crystal that satisfies these performances. That is, the present invention was achieved through extensive research into a liquid crystal compound that is a combination of a chemically stable ester compound and an optically active group having two asymmetric carbon atoms. In particular, the bonding mode between the two asymmetric carbons and the six-membered ring such as benzene that constitutes the skeleton of the liquid crystal compound is closely related to the spontaneous polarization and the temperature range in which the chiral smectic C phase is exhibited. The inventors have found that the helical pitch can be controlled by linking asymmetric carbon atoms with multiple methylene chains, and the above object has been achieved.

One aspect of the present invention is the general formula [1] [wherein R1 is an alkyl group or alkenyl group having 3 to 14 carbon atoms, R2 and R3 are lower alkyl groups having 1 to 3 carbon atoms,
R4 represents an alkyl group having 1 to 10 carbon atoms, Q1, Q2
, Q3 represents a single bond, (thio)ether bond, (thio)carboxylic acid ester bond, carbonyl bond or carbonyldioxy bond, n represents an integer of 2 to 6, M represents a bond, (thio)carboxylic acid -1,4-diyl homologous or chiaromatic six-membered ring that shows an ester bond, methyleneoxy bond, or ethylene bond, and each of which may have 1 or 2 oxygen atoms or nitrogen atoms as ring constituent atoms ′! !
;i) is shown. Further, carbons marked with * mean asymmetric carbons. ] and the above-mentioned optically active compound at least IF! The present invention relates to a liquid crystal composition containing the above.

Another aspect of the present invention relates to a liquid crystal light modulator using the above liquid crystal composition.

The above compound [1] can be divided into the following compounds [I'] and [I'] based on the basic skeleton M.

The alkyl group having 3 to 14 carbon atoms represented by R1 in the above compounds [1], [I'], and [I'] may be either linear or branched, and specifically, for example, , proyl, butyl, pentyl, hexyl, hebutyl,
Straight chain alkyl groups such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, etc., e.g. isobrovir, isobutyl, SQC-butyl, tart
-butyl, isobentyl, neobentyl, tart-bentyl, isohexyl, 1-methylpentyl, 2-methylbentyl, 5-methylhexyl, 2.3.5-trimethylhexyl, 2,7.8-trimethyldecyl, 4-ethyl Branched alkyl groups such as -5-methylnonyl can be mentioned. Among these, linear alkyl groups having 6 to 12 carbon atoms, such as hexyl, heptyl, octyl, decyl, undecyl, and dodecyl, are preferred.

Further, the alkenyl group having 3 to 14 carbon atoms may be either straight chain or branched, and specifically includes, for example, bropenyl, butenyl, bentenyl, hexenyl, heptenyl, octenyl, nonel, decenyl, undecenyl. , straight chain alganyl groups such as dodecenyl, tridecenyl, tetradecenyl, isopropenyl, isoallyl (isobutenyl), SCC-butenyl, tCrt-butenyl,
Mention may be made of branched alkenyl groups such as isopentenyl, tcrt-pentenyl, isohexenyl, 1-methylpentenyl. Among them, straight chain and carbon number 6
-12 akenyls are preferred, such as hexenyl, hebutenyl, octenyl, decenyl, undecenyl, dodecenyl.

Examples of the lower alkyl group having 1 to 3 carbon atoms represented by R2 and R3 include linear or branched alkyl groups such as methyl, ethyl, probyl, and isoprobyl. Among them, methyl is preferred.

The 1 to 10 alkyl group represented by R4 may be linear or branched, and specifically includes, for example, methyl, ethyl, proyl, butyl, pentyl, hexyl, heptyl, octyl, Straight chain alkyl groups such as nonyl, decyl, and also for example isopropyl, isobutyl, scc-butyl, tort-butyl, isopentyl, neobentyl, tCrt-pentyl, isohexyl,
Branched alkyl groups such as 1-methylpentyl, 2-methylbentyl, 5-methylhexyl, 4-ethylhexyl, 2.3.5-}limethylhexyl, 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 (thio)carboxylic 0 11 acid ester bond represented by Ql1Q2 and Q3 include a -C-0 (S) one 0 11 forward ester bond and a -(S)O-C- reverse ester bond. can.

Among various combinations of Q1 to Q3, Q1 is preferable.
is a single bond, a (thio)ether bond, or a forward ester bond, Q2 is a forward ester, a reverse ester, or a (thio)ether bond, and Q3 is a (thio)ether bond, a forward ester, or a reverse ester.

In addition, as the (thio)carboxylic acid O 11 stellate bond represented by X1Y, -C-0 (S) one forward ester bond and -<S> Examples of the methyleneoxy bond include a -CH20- bond and an -OCH2- bond.

Specifically, the six-membered ring-1,4-diyne group represented by is, for example, p-phenylene, 1,4-cyclohexylene, 2,5-(1,3-dioxane)diyl, 2,5-
Pyridinediyl, 2,5-pyrimidinediyl, 2,5-
(1,4-pyrazine)diyl, 3.6- (1.2-
pyridazine)diyl, etc., and these rings may be substituted with halogen, cyan, methyl, or methoxy.

can.

In this case, a preferred combination is that one of XSY is a single bond and the other is a (thio)carboxylic acid ester bond, and may be the same or different.

2. When the bond of 5-(1.3-dioxane)diyl is p-phenylene or one of the bonds is 2,5-pyrimidinediyl, a preferred combination is that X is monoviscous. Examples of the bonding mode of 2,5-pyridinediyl include R, -Q, -M-COOH nylene, or one in which one is 2,5-pyrimidinediyl.

These compounds [1] have two asymmetric carbon atoms in the molecule, and therefore have 48 optical nonamers, that is, (R
．． R), (R, S), (S, R) and (S,
S) type exists.

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

Method 1: Compound where Q2 is a forward ester bond O 11 (-C-0-) Reaction formula 1 [R1 to R4, Q1, Q3 and M have the same meanings as above. The same applies below] As shown in Reaction Formula 1, compound [1] can be obtained by subjecting carboxylic acid [111 and optically active dichiral alcohol [m] 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 [11 and dichiral alcohol [m],
A condensation reaction is carried out 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, p-luenesulfonic acid, benzenesulfonic acid,
H-organic sulfonic acids such as trifluoromethanesulfonic acid and methanesulfonic acid, or strongly acidic ion exchange resins such as Amberlyst ■ can be used. The same goes for thiocarboxylic acid, which can be synthesized by reacting thiocarboxylic acid with dichiral alcohol. 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 alcohol, tetrahydrofuran, dioxane, etc.), ethyl acetate, acetonitrile, dimethylformamide, etc. can be used. Carboxylic acid [111] is induced into an acid halide using a halogenating reagent such as phosphorus pentachloride, thionyl chloride, thionyl bromide, etc., and this halide is converted to dichiral alcohol [111] in the above organic solvent.
111 in the presence of a tertiary amine such as pyridine or triethylamine. In addition, alcohol [ml] is trimethylsilyl ether derivative K2
After leading to K a , this can also be condensed with an acid halogenated derivative of carboxylic acid [II] in the presence of a Lewis acid (for example zinc chloride). The same applies to thiocarboxylic acids.

Also, for example, N,N-dicyclohexylcarbodiimide (DCC), Mukaiyama reagent represented by 1-methyl-2-halobyridinium iodide, diethyl ester of azodicarboxylic acid (DEAD) and triphenylfusphine (Ph3P). The reaction between carboxylic acid [11] and alcohol [ml] can also proceed by using a combination with (so-called Mitsunobu reagent) or an activating reagent such as triphenylphosphine dipromide.

These methods are described, for example, in the journal Organic Chemistry 27.4675 (1962): Tetrahedron Letters, 1978.4475: Chemistry
Letters, 1975.1045: Chemistry Letters, 1976.13: Bulletin Chemical Society Japan, 50.1863 (1977). Bulletin Chemical e-Society ●Japan. 40.2
380 (1967): Synthetic Communication, 16.1423 (1986): Synthetic Communication, 16,659 (1986).

Method 2: Compound where Q2 is a reverse (thio)ester bond O 11 (-0 (S) 1C-) Reaction formula 2 is a known reaction, and the reaction can proceed using the conventional means described above. .

The reaction can proceed in the same manner with optically active dichiralthiocarboxylic acid.

Method 3: Compound where Q2 is a (thio)ether bond Reaction formula 3 As shown in Reaction formula 2, a hydroxyl group-containing compound [IV] and an optically active dichiral carboxylic acid [V] are subjected to a synthesis reaction to form a compound [ 1] can be obtained. In this condensation reaction, the reaction itself is as shown in formula 3,
Compound [11] can be obtained by subjecting hydroxyl group- or thiol group-containing compound [IV] and optically active dichiral alcohol [m] to an etherification reaction 64. 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) (Bittner et al., Chemical ● & Industries, 1975.281).

Alternatively, dichiral alcohol [ml] and organic sulfonyl chloride can be mixed with hydrogen such as pyridine or triethylamine.
The corresponding organic sulfonic acid ester may be obtained by reacting in an organic solvent in the presence of an organic base or an inorganic base such as sodium hydride, and this ester may be reacted with the hydroxyl group- or thiol group-containing compound [IV]. 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, 0-toluenesulfonic acid chloride, p-chlorobenzenesulfonic acid chloride, and benzenesulfonic acid chloride.
Examples include aromatic ring sulfonic acid chlorides such as chloride, α-naphthalenesulfonic acid chloride, and β-naphthalenesulfonic acid chloride, and aliphatic sulfonic acid chlorides such as methanesulfonic acid chloride and trifluoromethanesulfonic acid chloride.

Examples of H 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, fucetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (D
MSO), hexamethyl phosphate triamide (HMPA)
) etc.

Dichiral alcohol [I1[]
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 Cm. The halogen compound thus obtained and the hydroxyl group-containing compound [IV] can be reacted in an organic solvent in the presence of the above-mentioned inorganic base or organic base.

The target product [11] recovered 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 [■], [m], [IV], and [V] for producing the optically active compound [11 of the present invention] are all known substances or can be easily derived from known substances. be able to. For example, the optically active dichiral compounds [m] and [V] represented by the following general formulas can be derived from known optically active dichiral compounds, and are particularly asymmetrically synthesized by chemical methods (Morrison et al. Volume 1 (198
Volumes 3)-5 (1985); Bosnitsch et al. Asymmetric catalyst (1986); Shutter et al., Annaren, 1
983.939), asymmetric synthesis by biological methods using enzymes and microorganisms [Jones et al., “Applications of Biochemical Systems in Organic Chemistry, New York (1976); etc. Tetrahedron, 40
．． 1269 (1984): Hoffman et al. Chemisier Beliichte, 114, 2786 (1981); Nakamura et al., Tetrahedron Letters, 27.3155 (19
86)], optical resolution [Jackuz et al., “Etentiomers Racemates ◆ and ◆ Resolutions John Wiley and Sons (1981); Ingersoll, Organic Synthesis. Collective Volume,
2,506 (1943) Noheiyo. It can also be dehydrated by a method such as Chemistry Letters, 1981, 875.9511.

[In the formula, Q3, R2, R3, R4 and * have the same meanings as above,
2 represents a hydroxyl group or a thiol group [i.e., in the case of compound [111]], or a carboxyl group or a thiocarboxyl group [i.e., in the case of compound [V]].

The thus obtained compound [m], EV] can also be converted into other optical isomers by inverting the configuration on the asymmetric carbon by a chemical or biological method. 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 an intermolecular nucleophilic substitution reaction [Courley et al., Tetrahedron Letters, 1
975.3183; Sawyer and Gibbian, Tetrahedron, 35.1471 (1979); Kruisinga et al., Journal Organ Chemistry, 46,
4321. (1981); Hoffman and Desai,
Synthetic, Communication, 13.553
(1978)], or by activating an optically active secondary alcohol using N,N'-dicyclohexyllupodiimide (DCC) in the presence of cuprous chloride, and then reacting with an appropriate carboxylic acid. How to invert [Kauren, Angewante. Hemie, 99,800 (1987
)], or a method of inversion by reacting diethyl ester of azodicarboxylic acid (DEAD), triphenylphosphine (Ph3P), and a suitable carboxylic acid with an optically active secondary alcohol [Mitsunobu & Eguchi, Bretain Chemical Society・Japan, 44.34
27 (1971)]; Mitsunobu. synthesis, 19
81.1] etc. are known.

Typical examples of the optically active dichiral secondary alcohol [I [I] and the optically active dichiral carboxylic acid [V], which are important raw materials for constructing the dichiral moiety of the optically active compound of the present invention, are as follows. can be mentioned. n-
Case 2 will be specifically shown as an example.

A. Optically active dichiral secondary alcohol [ml (1)
When Q is an ether bond and R2 and R3 are both methyl groups: When both are methyl groups: 0 When R4 is a CI-10 alkyl group, that is, as 5-alkyloxy-2-hexanol, specifically For example, 5-methoxy 2-hexanol, 5-ethoxy 2-hexanol, 5-broboxy 2-hexanol, 5-ptoxy-2-hexanol, 5-pentyloxy-2-hexanol, 5-hexyloxy-2-hexanol, 5-heptyloxy-2-hexanol, 5
-Octyloxy-2-hexanol, 5-nonyloxy-2-hexanol, 5-decyloxy-2-hexanol, etc., or 5-isopropoxy-2-hexanol, 5-isoptoxy-2-hexanol, 5-
tert-butoxy 2-hexanol, 5-(2-
methylpentyloxy)-2-hexanol, 5-(
Examples include 3-methylbentyloxy)-2-hexanol.

(2) When Q is a forward ester bond, R2 and R3 are 3, and R4 is a Cl-10 alkyl group, specifically, as an alkyl ester of 5-hydroxy-2-methylhexanoic acid, for example, 5-hydroxy -2-methylhexanoic acid methyl ester, 5-hydroxy-2-methylhexanoic acid ethyl ester, 5-hydroxy-2-methylhexanoic acid proyl ester, 5-hydroxy-2-
Methylhexanoic acid butyl ester, 5-hydroxy-2
-Methylhexanoic acid pentyl ester, 5-hydroxy-2-methylhexanoic acid hexyl ester, 5-hydroxy-2-methylhexanoic acid hexyl ester, 5-hydroxy-2-methylhexanoic acid octyl ester, 5
-hydroxy-2-methylhexanoic acid nonyl ester,
5-hydroxy-2-methylhexanoic acid decyl ester, etc., or 5-hydroxy-2-methylhexanoic acid isopropyl ester, 5-hydroxy-2-methylhexanoic acid isobutyl ester, 5-hydroxy-2-methylhexanoic acid Lert- Examples include butyl ester, 2-methylpentyl 5-hydroxy-2-methylhexanoate, 3-methylpentyl 5-hydroxy-2-methylhexanoate, and the like.

(3> When Q is a reverse ester bond and R and R3 are both methyl groups: 0 noroxy-2-hexanol, 5-octanoyloxy-2-hexanol, 5-nonanoyloxy-2-hexanol, 5-decyloxy-2 -Hexanol, etc.
Or 5-isobutyloxy-2-hexanol, 5
-isovaleryloxy-2-hexanol, 5-pivaloyloxy-2-hexanol, and the like.

B. Optically active dichiral carboxylic acid [V] (1) Q
is an ether bond, and R2 and R3 are both methyl groups: When R4 is Cl-10 alkyl, that is, as 5-acyloxy-2-hexanol, for example, 5-acetyloxy-2-hexanol -A: Xanol, 5-propionyloxy-2-hexanol, 5-butyryloxy-2-hexanol, 5-pentanoyloxy-2-
When hexanol, 5-hexanoyloxy-2-hexanol, 5-hebuta R4 is a Cl-10 alkyl group,
That is, specific examples of 5-alkyloxy-2-methylhexanoic acid include 5-methoxy-2-methylhexanoic acid, 5-ethoxy-2-methylhexanoic acid, and 5-ethoxy-2-methylhexanoic acid.
Proboxy-2-methylhexanoic acid, 5-butoxy-2
-Methylhexanoic acid, 5-bentyloxy-2-methylhexanoic acid, 5-hexyloxy-2-methylhexanoic acid, 5-heptyloxy-2-methylhexanoic acid, 5-
Octyloxy-2-methylhexanoic acid, 5-nonyloxy-2-methylhexanoic acid, 5-decyloxy-
2-methyl hexanic acid, etc., or 5-isobroboxy-2-methylhexanoic acid, 5-isobutoxy-2-methylhexanoic acid, 5-tert-butoxy-2-methylhexanoic acid, 5-(2-methylpentyloxy)- 2
-methylhexanoic acid, 5-(3-methylpentyloxy)-2-methylhexanoic acid, and the like.

(2) When Q is a reverse ester bond and R and R3 are both methyl groups: 0 When R4 is a CI-10 alkyl group, that is, as 5-acyloxy-2-methylhexanoic acid, specifically, ,
For example, 5-acetyloxy-2-methylhexanoic acid, 5
-probionyloxy-2-methylhexanoic acid, 5-butyryloxy-2-methylhexanoic acid, 5-pentanoyloxy-2-methylhexanoic acid, 5-hexanoyloxy-2-methylhexanoic acid, 5-heptanoyloxy- 2-methylhexanoic acid, 5-octanoyloxy-2
-Methylhexanoic acid, 5-nonanoyloxy-2-methylhexanoic acid, 5-decyloxy-2-methylhexanoic acid, etc., or 5-isobutyryloxy-2-methylhexanoic acid, 5-isovaleryloxy-2- Examples include methylhexanoic acid and 5-bivaloyloxy-2-methylhexanoic acid.

Further, in the case of n'' 3 to 6, optically active dichiral secondary alcohols [nl] and optically active dichiral carboxylic acids [V] represented by the following general formulas are exemplified.

C. Optically active dichiral secondary alcohol [m] (1)
When Q is an ether bond and R2 and R3 are both methyl groups: (R4 "Anolequinol of Cl-10), that is, in the case of n-3, 6-alkyloxy-2-heptanol, n-4
In the case of 7-alkyloxy-2-octanol, n-
In the case of 5, 8-alkyloxy-2-nonanol is exemplified, and in the case of n-6, 9-alkyloxy-2-decanol is exemplified.

(2) When Q is a forward ester bond and R2 and R33 are both methyl groups: 0 (R4 ``alkyl of Cl-10'') That is, in the case of n-3, 6-hydroxy-2-methylhebutanoic acid alkyl ester, For n-4, alkyl 7-hydroxy-2-methyloctanoate, for n-5, alkyl 8-hydroxy-2-methylnonanoate, and for n-6, alkyl 9-hydroxy-2-methyldecanoate. Examples include esters.

(3) When Q is a reverse ester bond and R2 and R33 are both methyl groups: 0 (R4 "alkyl of Cl-10"), that is, when n "3, 6-acyloxy-2-heptanol, when n-4 , 7-acyloxy-2-octanol, when n=5, 8-acyloxy-2-nonanol, and when n-1-6, 9-acyloxy-
D. 2-decanol is exemplified, respectively. Optically active dichiral carboxylic acid [V] (1) Q
When 3 is an ether bond and R2 and R3 are both methyl groups: (R4 "alkyl of CI-10") That is, in the case of n-3, 6-alkyloxy-2-monomethylhebutanoic acid, in the case of n-4 , 7-alkyloxy-2-
Examples include methyloctanoic acid, 8-alkyloxy-2-methylnonanoic acid for n-5, and 9-alkyloxy-2-methyldecanoic acid for n-6.

(2) When Q is a reverse ester bond and R2 and R33 are both methyl groups: In the case of 0-6, 9-acyloxy-2-methyldecanoic acid is exemplified.

It goes without saying that compounds with combinations of Q2 and Q3 other than those mentioned above can also be synthesized by known means.

Next, we will give specific examples of carboxylic acids [■] and alcohol or phenolic hydroxyl-containing compounds [VI], which are important raw materials for constructing the skeleton of the optically active compound of the present invention. explain.

The raw material carboxylic acid [■] can be roughly classified into compounds represented by the following general formula.

(R4 ``Alkyl of CI-10) That is, in the case of n-3, 6-acyloxy-2-methylhebutanoic acid, in the case of n-4, 7-acyloxy-2-methyloctanoic acid, in the case of n-5, 8-acyloxy-2-
methylnonanoic acid, and such compounds such as 4-(4'-alkyloxy or alkyl-4-biphenyloxycarbonyloxy)benzoic acid, 4-(4'-alkyloxy or alkyl-4-biphenyloxycarbonyl)benzoic acid, Examples include 4'-(4-alkyloxy or alkylphenylcarbonyloxy)-4-biphenylcarboxylic acid, 4'-(4-alkyloxy or alkylphenyloxycarbonyl)-4-biphenylcarboxylic acid, and the like. Further, for example, 4'-alkyloxy (or alkyl)-4-biphenylcarboxylic acid, 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 alkyl birimidinyl-
2-oxycarbonyl)biphenyl-4-carboxylic acid,
4'[2-(5-alkyloxy or alkyl-21pyridyl)ethyl]biphenyl-4-carboxylic acid, 4-
[4-(}Ransu-5-alkyloxy or alkyl-1,3-dioxan-2-yl)phenylcarbonyloxy]benzoic acid, 4'-[4-(trans-5
-Alkyloxy or alkyl-1,3-dioxane-
2-yl)]biphenyl-4-carboxylic acid, or for example 2-[4-(4-alkyloxy or alkylphenylcarbonyloxy)phenyl]virazinyl-5-
carboxylic acid, 2-(4'-alkyloxy or alkyl-4-biphenyl)virazinyl-5-carboxylic acid,
4'-(5-alkyloxy or alkylpyrazinyl-2-oxycarbonyl)biphenyl-4-carboxylic acid, 4'-(6-alkyloxy or alkyl-3
-pyridazinyl)biphenyl-4-carboxylic acid and the like.

Further, the raw material compound [IV] can be roughly classified into compounds represented by the following general formula.

Such compounds include, for example, 4-hydroxyphenyl esters of 4'-alkyloxy or alkylbiphenyl-4-carboxylic acids, 4-hydroxyphenyl esters of 4'-hydroxybenzoic acid,
'-alkyloxy or alkyl-4-biphenyl ester, 4' of 4-alkyloxy or alkylbenzoic acid
-hydroxy-4-biphenyl ester, 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-(5-hydroxy-2-pyrimidinyl)phenyl ester of alkyloxy or alkylbenzoic acid, 2-(4'-alkyloxy or alkyl-4-biphenyl)pyrimidin-5-ol,
5-alkyloxy or alkyl-2-pyridinyl ester of 4'-hydroxy-4-biphenylcarboxylic acid,
4'-[2-(5-alkyloxy or alkyl-2-biridyl)ethyl]biphenyl-4-ol, 4
- [4-(1-trans-5-alkyloxy or alkyl-1,3-dioxane-2-yne)]4-hydroxyphenyl ester of benzoic acid, 5 of 4'-hydroxy-4-biphenylcarboxylic acid -alkyloxy or 5-alkyl-2-virazinyl esters.

Regarding the thiocarboxylic acid [11] and the thiol or thiophenol compound [IV], thiol or thiophenol compounds analogous to the above-mentioned compounds can be mentioned.

As described above, optically active dichiral alcohols, optically active dichiral carboxylic acids, skeleton carboxylic acids, skeleton (thio)phenolic hydroxyl group compounds, skeleton, which are optically active dichiral side chain compounds contained in the optically active compound of the present invention. Representative examples of (thio)alcohols are listed. Specific examples of the optically active compound of the present invention will be described below, but the invention is not limited to these examples, and the optically active compound can be produced by appropriately combining the above-mentioned skeleton component and optically active dichiral component. . For example, specific examples include the compounds shown below.

0 The optically active compound [1] of the present invention has a structure in which an asymmetric carbon atom is bonded to oxygen, sulfur, or (thio)carbonyl, and therefore generally exhibits high spontaneous polarization. Further, most of the compounds exhibit a liquid crystal phase suitable for a display system utilizing ferroelectricity, that is, a chiral smectic C (Sc'') phase, and are characterized by having a wide temperature range at low temperatures.

Furthermore, the optically active compound of the present invention is extremely stable against heat, light, moisture, and air. Therefore, when the compound of the present invention is put to practical use as a liquid crystal material, it is possible to eliminate the need for installing an overheating prevention device and the need for a frit seal to prevent moisture absorption and permeation.

Although the optically active compound [1] of the present invention may be used as a liquid composition, conventionally known liquid crystal compounds such as ship base-based, biphenyl-based, phenylcyclohexane-based, and heterocyclic-based liquid crystal compounds may also be used. By blending these liquid crystal compounds, it is possible to obtain a liquid crystal composition exhibiting excellent properties.

Examples of these liquid crystal compounds that can be blended with the optically active compound [I] of the present invention include ferroelectric liquid crystal compounds and liquid crystal compounds exhibiting a smectic C phase. As the ferroelectric liquid crystal compound, for example, Biff-K2 type liquid crystals described in JP-A-59-118744 and JP-A-60-13729, JP-A-59-128357, etc.
, ester type liquid crystals described in JP-A-60-51147, JP-A-61-22051, JP-A-61-249953, JP-A-60-260564, JP-A-61-24756, JP-A-61-
Examples include pyrimidine-type liquid products described in 85368 and 61-215373. In addition, examples of liquid crystal compounds exhibiting a smectic C phase include, for example, JP-A No. 6
The ester-type liquid crystal compound described in Publication No. 2-228036, the 16th Freiburger Liquid Product Symposium (1986)
, 3.21) and the materials of the 1st International Symposium on Codielectric Liquid Crystals (September 21, 1987).

In addition, the liquid crystal composition according to the present invention is based on the above-mentioned optically active compound of the present invention as shown in "Liquid Crystal List" l and ■ (V E
B Vcrlag. It can be prepared by arranging nematic liquid crystals, cholesteric liquid crystals, etc. described in ``Lclpz1g'', and may also be prepared by blending with commercially available nematic liquid crystals. In particular, a liquid crystal composition containing an optically active compound and a nematic liquid crystal according to the present invention has the advantage that the twist direction of the cholesteric pitch and the length of the pitch 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.
06 may be blended in an amount of 1 to 5% by weight when preparing a nematic liquid crystal composition.

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 devices. Examples include terminal display boards.

Although various types of liquid crystal display elements are known, any display element may be used as long as the liquid 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. JP-B-63-22287, U.S. Patent No. 4,56
The elements disclosed in No. 3,059 and the like 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.

[Failure to implement] The present invention will be specifically described below with reference to Examples.

The phase series, phase transition temperature, and spontaneous polarization value of the optically active compounds produced in Examples were all determined. The measurement results are shown in Table 1. It was shown to.

The phase series and phase transition temperature were measured using a polarizing microscope and DS.
This was done using C.

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

Each liquid crystal phase is indicated by the following symbol.

Iso: Isotropic phase N: Chiral nematic phase-S
A: Smectic A phase K: Crystal phase S *:
Chiral smectic C phase C S1, S2: Reference example 1 of smectic phase that is difficult to identify. (2
3.5S)-5-alfoxy-2-hexanol production literature [G. K. (23,5S)-2.5hexanediol was obtained by reducing 2.5-hexanedione with Ban's yeast according to the method of Heiser Synthetics, Communication, 13.765 (1983). This product was reacted with the corresponding molar amount of alkyl iodide in the presence of an equimolar amount of oily sodium hydride (content about 60%) in N,N-dimethylformamide (DMF) to obtain the title compound as an oil.

(R-zen CH3, C3H, , C4H9, C8Hl
7) R Yield (%) CH3 37.1 CI{ 49.2 37 C4H9 60.7 As a representative physical constant, the lH-NMR spectrum of (2S.5S)-5-methoxy-2-hexanol is shown below.

'H-NMR (90M] Iz, CD Cff
a) δ: 1.15 (3H, d, J■6.
3H), 1. 18 (3d, d. J
-6. 3Hz). 1. 54 (4H,t
, J-2. 8Hz), 2. 46 (IH.
borad s), 3. 32 (H, s)
, 3. 35 (11, m), 3.75
(IH, m).

Reference example 2. (2R,5S)-5-Butoxy 2-hexanol Production Reference Example 1 Mitsunopu and E, Eguchi, Pretain. Chemical, Society. Bayaban. 44, 3427 (1971)] and inversion afforded the title compound.

0H oc-ph 11 0 hydrolyzed OBu; that is, (2S,5S)-5-butoxy-2-hexanol 1.23 g. Benzoic acid 0. 86 g and triphenylphosphine 2.78. 25ml of dry ether
Dissolve diethyl azodicarboxylate (DEAD) in 2.
29 g was added dropwise at room temperature while stirring. After stirring at room temperature for 1 hour, the reaction solution was concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (elution solvent: dichloromethane), and benzoic acid (2R,
5S)-5-butoxy 2-hexyl ester 1.56
g was obtained as a colorless oil. 1.2 g of this product was dissolved in 20 ml of methanol, and 516 ml of IN methanol solution of sodium hydroxide was added dropwise at room temperature while stirring. After stirring at room temperature for 8 hours, 15 ml of water was added to the reaction solution, and the mixture was further stirred for 8 hours.

Add water to the reaction solution and extract with dichloromethane.

The extract was dried and concentrated, and the residue was subjected to Kugel distillation under reduced pressure to obtain 0.57 g of the title compound as a colorless oil.

”H-NMR (90MIIz, CDCfl 3
) δ: 0, 92 (3H, t, J-6. 5
11z), 1. 14 (3H, d, J=
6. Ollz), 1. 18 (3H, t.
J-6. Ollz), 1.40-1.70 (10H,
m) +2. 41 (IH, broad
s), 3. 21-3.59 (3H, m). 3
．． 62-3.93 (IH, m).

Reference example 3. (2R,5S)-2-methyl-5-proboxyhexanoic acid Reference example 1? υ(2R,5S)-5-proboxy2
-Synthesized using hexanol as a starting material according to the following route.

CN, i.e., (2S,5S)-5-propoxy-2-hexanol 1.45g and methanesulfonylchloride 1
．． 0.9 g of triethylamine was dissolved in 10 ml of dichloromethane, and 0.96 r of triethylamine was added dropwise while stirring under water cooling. After stirring for 4 hours under water cooling, the reaction solution was poured into water and the organic layer was separated. This organic layer was washed with dilute hydrochloric acid and deuterated water, dried, and concentrated to obtain 1.98 g of crude mesylate as an oil. This product is dimethyl sulfoxide (DMSO)
), add 1.7 g of sodium cyanide, and stir at 60°C for 2 hours. Pour the reaction solution into water and extract with dichloromethane. Dry and concentrate the extract,
The residue was separated by silica gel column chromatography [elution solvent: n-hexane-ethyl acetate (9:1)].
Purification yielded 1.8 g of (2R,-5S)-2-methyl-5-proboxybencunitrile as a colorless oil.

Dissolve 1.8 g of this compound in 30 ml of dry toluene and add diisobutylaluminum hydride (D I BAL
) toluene solution (1.5 mol%) at -78°C.
It was added dropwise while stirring. After stirring at -78°C for 30 minutes, 1 ml of concentrated hydrochloric acid was added dropwise to the reaction mixture while stirring, then diluted hydrochloric acid was added, and the organic layer was separated. The organic layer was concentrated under reduced pressure to obtain a crude aldehyde as an oil. Dissolve this product in 50ml of acetone and use Jones reagent (Jones reagent).
nes' reagent) was added dropwise while stirring under ice-cooling. Pour the reaction solution into water and extract with dichloromethane. The extract was dried and concentrated, and the residue was subjected to Kugel distillation under reduced pressure to obtain 0.88 g of the title compound as a colorless oil.

'H-NMR (90MIIz, CDCIa)
δ: 0.92 (3H, t, J-7.611z).
1,13 (3H, d, J=6.Ollz),
1. 19 (3H, d, J-6.811z) 1
．． 32 ~ 1.93 (6H, m), 2.20 ~ 2.6
3 (IH, m), 3.14-3.59 (3H, m)
.

IRI/n0atcm-': 1710. 1470
．． lax 1090. Example 1 4'-[(IR,4S)-1-methyl-4-methoxypentyloxy]-4-biphenylcarboxylic acid 4-octyloxyphenyl ester (2S,5S)-5 produced in Reference Example 1 -Methoxy 2
-hexanol 0.26g, 4'-hydro-4-
0.8 g of biphenylcarboxylic acid 4-octyloxyphenyl ester and 0.9 g of triphenylphosphine were dissolved in 30 ml of dry tetrahydrofuran, and 0.61 g of diethyl aphidicarboxylate was added dropwise. The mixture was stirred at room temperature for about 1 hour and then concentrated under reduced pressure. The residue was separated and purified by column chromatography [silica gel, developing solvent: carbon tetrachloride monoethyl acetate (20:1)], and then recrystallized from methanol to obtain 0.14 g of the title compound.

The elemental analysis values of this compound are shown below.

Elemental analysis value calculation value (as C33H4205): C 7 (1.66
; H 8.33 fruit 815ffl:
C 76.54. H 8Jl Example 2 4' -
[(IR,4S)-1-methyl-4-propoxybentyloxy]-4-biphenylcarboxylic acid 4-octyloxyphenyl ester (2S,5S)-5-proboxy- produced in Reference Example 1
2-hexanol 0.34. and 4'-hydroxy-4-
Using the same method as in Example 1 from 0.8 g of biphenylcarboxylic acid 4-octyloxyphenyl ester, 0.534.
The title compound was obtained.

The elemental analysis values of this compound are shown below.

Elemental analysis value = 1 calculated value (as 036H4805): C 77.11
．． H 8.63 Actual value: C 77.
21. H 8.84 length Example 3 4' - [(I
R,4S)-1-methyl-4-broboxypentyloxy]-4-biphenylcarboxylic acid 4-octyloxyphenyl ester (2S.5S)-5-butoxy 2 produced in Reference Example 1
-Hexanol 0.37r and 4'-hydroxy-4-biphenylcarboxylic acid 4-octyloxyphenyl ester 0.8g in the same manner as in Example 1 to obtain 0.394. The title compound was obtained.

The elemental analysis values of this compound are shown below.

Calculated elemental analysis value (as C37H5oO5): C 77.31.
H 8.77 Actual value: C 77.4
1. H 8.81 length Example 4 4' - [(IR
,4S) -1-methyl-4-octyloxypentyloxy]-4-biphenylcarboxylic acid 4-octyloxyphenyl ester (2S,5S)-5-octyloxy-2-hexanol produced in Reference Example 1 0.48 ．． and 4'-hydroxy-
From 0.8 g of 4-octyloxyphenyl 4-biphenylcarboxylate to 0.14 g in the same manner as in Example 1.
1 g of the title compound was obtained.

The elemental analysis values of this compound are shown below.

Elemental analysis value calculation value (as C4lH5905): C 77.93;
H 9.41 Actual value: C 78.1
B. H 9.33 Example 5 4- [(IR,4
S)-1-Methyl-4-methoxypentyloxy] monobenzoic acid 4'-octyloxy-4-biphenylyl ester 0.28 g of (2S,5S)-5-methoxy-2-hexanol produced in Reference Example 1 and -Hydroxybenzoic acid 4'-octyloxy-4-biphenylyl ester 0
．． 0.70 g of the title compound was obtained from 8 g in the same manner as in Example 1.

The elemental analysis values of this compound are shown below.

Elemental analysis value calculation value (as C34H4405): C 76. (to
．． H 8.33 Tue 8p1 value: C
7B. 50. H L33 length Example 6 4-octyloxybenzoic acid 4'[(IR,4S)-1-methyl-4
-broboxybentyloxy]-4-biphenylyl ester produced in Reference Example 1 (2S.5S) -5-propoxy 2-hexanol 0.34. and 0.8 g of 4-octyloxybenzoic acid 4'-hydroxy-4-biphenylyl ester in the same manner as in Example 1 to obtain 0.48r of the title compound.

The elemental analytes of this compound are shown below.

Elemental analysis value calculation value (as C36H4805): C 77.11
．． H 8.63 Actual value: C 77.
21. H 8.74 Example 7 4- [(IR,
4S)-1-methyl-4-broboxypentyloxy]
-4'-Octyloxybiphenyl (2S, 5S) produced in Reference Example 1 -5-proboxy-2-hexanol 0.47 g and 4-hydroxy-4'
-octyloxybiphenyl 0. Length example 1 from 8g
In the same manner as above, 0.311 g of the title compound was obtained.

The elemental analysis values of this compound are shown below.

Elemental analysis value calculation value (as C29H4403): C 79.04;
H 10.0G actual ilFJ value 2C 7
9.16; H 10.0g Example 8 4'-
[(Is,4S)-1-methyl-4-butoxypentyloxy]-4-biphenylcarboxylic acid 4-octyloxyphenyl ester Manufactured in Reference Example 2 (2R,5S)
-5-ptoxy-2-hexanol 0.37. and 4'-
0.495 sr of the title compound was obtained from 0.8 g of hydroxy-4-biphenylcarboxylic acid 4-octyloxyphenyl ester in the same manner as in Example 1.

The elemental analysis values of this compound are shown below.

Elemental analysis value: 1° calculated value (as C37H5oO5): C 77.31.
H 8.77 Length measurement: C 77.3
7. H 8.88 length Example 9 (2R, 5S)-2
-Methyl-5-butoxyhexanoic acid 4'-octyloxy-4-biphenylyl ester Manufactured by reacting (2R,5S)-2-methylolarproboxyhexanoic acid produced in Reference Example 3 with oxalyl chloride (2R ,5S)-2-methyl-5-propoxyhexanoyl chloride 0.35g and 4-hydronoxy-4
0.5 g of '-octyloxybiphenyl was reacted in THF in the presence of trienalamine. The reaction solution was treated in the same manner as in Example 1 to obtain 0.205 g of the title compound.

The elemental analysis values of this compound are shown below.

Elemental analysis value calculation value (as C3oH4405): C 78.8g,
H 9.4B Actual value: C 78.5
9. H 9.53 Example 10 3-[(IS,4
S)-1-methyl-4-proboxypentyloxy]
-6- (4-octyloxy)phenylpyridazine (2S,5S)-5-profoxy- obtained in Reference Example 1
Dissolve 320 μm (2.0 mmol) of 2-hexanol in 15 ml of anhydrous toluene, and add sodium metal at room temperature while stirring. This mixture contains 3chloro6-(4
-octyloxyphenyl)pyridazine 4 7 8 mg
(1.5 msol) was added, and the mixture was heated under reflux for 3 hours. After cooling the reaction mixture, water and toluene are added, and the toluene layer is separated. The toluene layer was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: 201 hexane-ethyl acetate-4:1) to obtain 190 mg of the title compound.

Length Examples 11 to 18 By the same operation as in Length Example 1, the raw materials constituting the corresponding skeleton parts and the corresponding dichiral compounds were reacted to form the table-
Compounds 11 to 18 shown in 1 were synthesized.

The following table summarizes the elemental analysis values of these compounds and the compounds synthesized in Examples 19 and 20.

Example 19 The title hexanoic acid was obtained using 0H Br (2S, 5S) -2-methyl-5-proxy-2-hexanol as a starting material.

(l1) Esterification The above (2S.5S)-2-methyl-5-propoxyhexanoic acid is reacted with oxalyl chloride, (2S,5S)-
2-Methyl-5-proboxyhexanoic acid chloride was obtained.

The title compound was synthesized in the same manner as in Example 9 using a compound having a skeleton moiety corresponding to this chloride.

Example 20 Polarization was 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.

(28.5S)-2-methyl-5 obtained in Reference Example 3
-Proboxyhexanoic acid was reacted with oxalyl chloride to obtain the corresponding acid chloride. Using the thus obtained compound having a skeleton corresponding to the acid chloride, the title compound was synthesized in the same manner as in Example 9.

Application Example A predetermined amount of the optically active compound of the present invention shown in the above example is blended into the conventionally known co-dielectric liquid compound (hereinafter referred to as base liquid crystal) shown in Table 2 to obtain the optically active compound of the present invention. A crude liquid crystal containing the liquid crystal was obtained.

Self-presentation of this composition and the base liquid crystal alone 2 Table 3 In addition, a cell made of Nesa glass spin-coated with polyimide and rubbed with a polyethylene terephthalate film (6 liters thick) as a substrate was used as a surface. A liquid crystal element was prepared by sealing the composition shown in 3. When a rectangular wave of 40 Vp-p was applied to this at room temperature and observed under a polarizing microscope, it was found that the element containing only the parent 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 its response was also extremely good.

Effects of the Invention As is clear from the examples and application examples, the present invention provides a liquid crystal compound or liquid crystal composition that has a large spontaneous polarization and exhibits a chiral smectic C phase. 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.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is an alkyl group or alkenyl group having 3 to 14 carbon atoms, and R_2 and R_3 are lower alkyl having 1 to 3 carbon atoms. group, R_4 represents an alkyl group having 1 to 10 carbon atoms, and Q
_1, Q_2 and Q_3 represent a single bond, (thio)ether bond, (thio)carboxylic acid ester bond, carbonyl bond or carbonyldioxy bond, n represents an integer of 2 to 6, M is ▲mathematical formula, chemical formula, There are tables, etc.▼X▲mathematical formulas, chemical formulas,
There are tables, etc.▼Y▲There are mathematical formulas, chemical formulas, tables, etc.▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼X▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (X and Y each represent a single bond, (thio)carboxylic acid ester bond, methyleneoxy bond, or ethylene bond, ▲ Numerical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ are allotropic or heterologous six-membered rings that may have 1 or 2 oxygen atoms or nitrogen atoms as ring constituent atoms - 1
, 4-diyl group). Further, carbons marked with * mean asymmetric carbons. ] An optically active compound represented by. 2. ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
are the same or different, p-phenylene, 1,4-cyclohexylene, 2,5-(1,3-dioxane)diyl, 2,
5-pyridinediyl, 2,5-pyrimidinediyl, 2,
5-(1,4-pyrazine)diyl or 3,6-(1,
2. The compound according to claim 1, which is 2-pyridazine)diyl. 3. M is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼X ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ Y , there are tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ are all compounds that are p-phenylene. 4. In the compound according to claim 1, where M is ▲There are mathematical formulas, chemical formulas, tables, etc.▼X▲There are mathematical formulas, chemical formulas, tables, etc.▼, where A compound in which both of ▼ are p-phenylene. 5. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_4 is an alkyl group having 1 to 10 carbon atoms, Q_
3 is a (thio)ether bond, (thio)carboxylic acid ester bond, carbonyl bond, or carbonyldioxy bond, n is an integer of 2 to 6, Z is a hydroxyl group, a thiol group,
Indicates a carboxyl group or a thiocarboxyl group. Also*
The marked carbons mean asymmetric carbons. ] A dichiral compound represented by. 6. The compound of claim 5, wherein n is 2. 7. A liquid crystal composition comprising at least one optically active compound according to claim 1 and optionally a host liquid crystal. 8. A liquid crystal light modulating device comprising the liquid crystal composition according to claim 7 disposed between at least one pair of substrates.