JP2805887B2 - Optically active phenylethanol derivative, method for producing the same, liquid crystal composition containing the same as active ingredient, and liquid crystal element using the same - Google Patents

Description

The present invention relates to a novel organic compound, a method for producing the same, a liquid crystal composition containing the same as an active ingredient, and a liquid crystal device using the same. The present invention relates to an optically active phenylethanol derivative useful as a compounding component of a dielectric liquid crystal composition, a method for producing the same, a liquid crystal composition containing the same as an active ingredient, and a liquid crystal device using the same.

<Prior Art> At present, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device. This TN liquid crystal display has many advantages such as low driving voltage and low power consumption. However, in terms of response speed, it is inferior to light-emitting display devices such as cathode-ray tubes, electroluminescence, and plasma displays. Torsion angle
A new TN type display element with a 180-270 degree angle has been developed, but the response speed is still inferior. Although various improvements have been made as described above, a TN display element having a high response speed has not been realized. However, a new display method using a ferroelectric liquid crystal, which has been actively studied recently, has a possibility of remarkably improving the response speed (Clark et al .: Applid Phys. Lett., 36 , 899 (1980)). .

This method is a method utilizing a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity (hereinafter abbreviated as Sc *). It is known that the phase exhibiting ferroelectricity is not only the Sc * phase, but also the phases such as chiral smectic F, G, H, and I exhibit ferroelectricity.

Many properties are required for ferroelectric liquid crystal materials used in ferroelectric liquid crystal display elements actually used, but at present, a single compound cannot satisfy such properties, It is necessary to use a ferroelectric liquid crystal composition obtained by mixing a liquid crystal compound or a non-liquid crystal compound.

Further, not only a ferroelectric liquid crystal composition comprising only a ferroelectric liquid crystal compound, but also Japanese Patent Application Laid-Open No. 61-195187 discloses non-chiral smectic C, F, G, H, I phases (hereinafter referred to as Sc). It is reported that a ferroelectric liquid crystal composition can be obtained by mixing a compound or a composition exhibiting a ferroelectric liquid crystal phase with a compound or a composition exhibiting a ferroelectric liquid crystal phase as a basic substance. Have been. Furthermore, a compound or composition exhibiting a phase such as Sc is used as a basic substance, and one or more compounds that are optically active but do not exhibit a ferroelectric liquid crystal phase are mixed to form a ferroelectric liquid crystal composition as a whole. also found (Mol.Cryst.Liq.Cryst. 89 .327 (198
2)).

Taken together, it can be seen that one or more optically active compounds can be mixed as a basic substance to form a ferroelectric liquid crystal composition regardless of whether or not it exhibits a ferroelectric liquid crystal phase. However, the optically active substance preferably exhibits a liquid crystal phase if desired, and when the optically active substance does not exhibit a liquid crystal phase, it is desirable that the structure is similar to a liquid crystal compound, that is, a pseudo liquid crystal substance. However, so far, no liquid crystal material has been found that waits for spontaneous polarization required for high-speed response and has liquid crystallinity in a lower temperature range.

<Problems to be Solved by the Invention> The present invention relates to a ferroelectric liquid crystal material having sufficient spontaneous polarization and exhibiting liquid crystallinity at a lower temperature range, or inducing sufficient spontaneous polarization and lowering the liquid crystallinity. It is intended to provide a ferroelectric liquid crystal material which brings about.

<Means for Solving the Problems> That is, the present invention provides a compound represented by the general formula (I): (Wherein, R ₁ represents an alkyl group having 3 to 20 carbon atoms, R ₂ represents an alkyl group or an alkoxyalkyl group optionally substituted with a halogen atom having 1 to 20 carbon atoms. X represents —CO
Y represents O- or -OCO-, and Y represents -COO- or -OCO-. p and l are 1 or 2, respectively, and m and s are 0 or 1. However, when m is 0, 1 and p are not 2 at the same time, and Y is -COO-. * Indicates an asymmetric carbon atom. ), A method for producing the same, a liquid crystal composition containing the same as an active ingredient, and a liquid crystal element using the same.

 Hereinafter, the present invention will be described in detail.

Optically active phenylethanol derivative (I) of the present invention
Can be prepared by the following method.

That is, the general formula (II) (Wherein, R ₁ , X, Y, 1, m, p and * have the same meanings as described above) and an optically active alcohol represented by the general formula (III) (In the formula, R ₂ represents an alkyl group or an alkoxyalkyl group which may be substituted with a halogen atom having 1 to 20 carbon atoms, and R ′ represents a hydroxyl group or a halogen atom.) It can be obtained by: The above-mentioned optically active alcohols (II) are novel compounds discovered by the present inventors for the first time, and can be produced, for example, by the following method.

(Wherein, R represents a lower alkyl group. Ar represents Is shown. Here, examples of the substituent R _{1 in} the general formula (II) include those having an alkyl group having 3 to 20 carbon atoms, and specific examples of the alkyl group are as follows.

Propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.

Examples of R ₂ in the general formula (III) include the following alkyl groups or alkoxyalkyl groups.

Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxy Butyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, Propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhex , Propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxy Ethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl,
Hexylhexylpentyl, hexyloxyhexyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxymethyl, octyloxyethyl, Octyloxypropyl,
Decyloxymethyl, decyloxyethyl, decyloxypropyl, 1-methylethyl, 1-methylpropyl,
1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 2
-Methylethyl, 2-methylbutyl, 2,3-dimethylbutyl, 2,3,3-trimethylbutyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylpentyl, 2,4
-Dimethylpentyl, 2,3,3,4-tetramethylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2,5-dimethylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylhexyl Trihalomethylpentyl, 2-trihalomethylhexyl, 2-trihalomethylheptyl, 2-haloethyl, 2-halopropyl, 3-
Halopropyl, 3-halo-2-methylpropyl, 2,3-
Dihalopropyl, 2-halobutyl, 3-halobutyl, 4
-Halobutyl, 2,3-dihalobutyl, 2,4-dihalobutyl, 3,4-dihalobutyl, 2-halo-3-methylbutyl, 2-halo-3,3-dimethylbutyl, 2-halopentyl, 3-halopentyl, 4- Halopentyl, 5-halopentyl, 2,4-dihalopentyl, 2,5-dihalopentyl,
2-halo-3-methylpentyl, 2-halo-4-methylpentyl, 2-halo-3-monohalomethyl-4-methylpentyl, 2-halohexyl, 3-halohexyl, 4-
Halohexyl, 5-halohexyl, 6-halohexyl,
2-haloheptyl, 2-halooctyl, halomethyl, 1
-Haloethyl, 1-halopropyl, 1-halobutyl, 1
-Halopentyl, 1-halohexyl, 1-haloheptyl, 1-halooctyl.

(Where the above-mentioned alkyl group in halo, fluorine, chlorine,. Bromine or iodine) in the above reaction, the carboxylic acid or their that as the carboxylic acids represented by the general formula (III) having these substituents R ₂ Acid halides such as acid anhydrides or chlorides, bromides are used.

In addition, these carboxylic acids or derivatives thereof may be any of a ceramic body and an optically active body.

Some of the above optically active carboxylic acids are obtained by oxidation of the corresponding alcohol, reductive deamination of the amino acid. Others can be derived from optically active amino acids and optically active oxyacids that are naturally occurring or obtained by resolution, such as:

Alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, alosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, trifluoroalanine, asparagine Acid, glutamic acid, lactic acid,
Mandelic acid, tropic acid, 3-hydroxybutyric acid, malic acid, tartaric acid, isopropylmalic acid and the like.

Optically active alcohols (II) and carboxylic acids (II
The reaction with I) is usually carried out in the presence or absence of a solvent,
It is generally performed in the presence of a catalyst.

When a solvent is used in this reaction, examples of the solvent include aliphatic or aromatic solvents such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, and hexane. Solvents which are inert to the reaction of group hydrocarbons, ethers, ketones, halogenated hydrocarbons and the like, alone or in a mixture. The amount can be used without any particular limitation.

In the case of using an acid anhydride or an acid halide of the above carboxylic acid in the reaction, the amount of the acid anhydride to be used must be at least one equivalent of the optically active alcohol (II), and the upper limit is not particularly limited. However, it is preferably 4 equivalent times.

Examples of the catalyst include dimethylaminopyridine, trimethylamine, tri-n-butylamine, pyridine,
Picoline, collidine, imidazole, sodium carbonate,
Organic or inorganic basic substances such as sodium methylate and potassium bicarbonate can be mentioned. Further, an organic acid or an inorganic acid such as toluenesulfonic acid, methanesulfonic acid, or sulfuric acid can be used as a catalyst.

In using such a catalyst, for example, when an acid halide of a carboxylic acid is used as a raw material, pyridine,
Triethylamine is particularly preferably used.

The amount of the catalyst used depends on the combination of the acid anhydride or acid halide of the carboxylic acid and the catalyst used, and is not necessarily specified. For example, when an acid halide is used, one equivalent of the acid halide is used. More than double.

When a carboxylic acid is used in the reaction, the carboxylic acid is dehydrated and condensed in the presence of a condensing agent, usually using 1 to 2 equivalents of the optically active alcohol (II) to obtain an optically active compound. A phenylethanol derivative (s = 1 in the general formula (I)) can be obtained.

As the condensing agent, carbodiimides such as N, N'-dicyclohexylcarbodiimide and N-cyclohexyl-N '-(4-diethylamino) cyclohexylcarbodiimide are preferably used. If necessary, organic bases such as 4-pyrrolidinopyridine, pyridine and triethylamine are used. Are used together.

The amount of the condensing agent to be used is 1 to 1.2 equivalent times relative to the carboxylic acid, and when a base is used, the amount to be used is 0.01 to 0.2 equivalent times to the condensing agent.

The reaction temperature is usually -30C to 100C, preferably -25C to 80C.

The reaction time is not particularly limited, and the time when the optically active alcohols (II) as the raw materials disappear can be regarded as the end point of the reaction.

After completion of the reaction, usual separation means such as extraction, liquid separation,
By an operation such as concentration, an optically active phenylethanol derivative (I) (where s = 1) can be obtained in good yield.
This can be purified by column chromatography, recrystallization, etc., if necessary.

Next, a method for producing an optically active phenylethanol derivative in which s is 0 in the general formula (I) will be described.

In the following description, the general formula X-R ₂ is an alkylating agent (wherein, R ₂ is .X showing a halogen atom in an alkyl group which may be substituted or an alkoxyalkyl group having 1 to 20 carbon atoms halogen Represents an atom or —OSO ₂ R, wherein R represents a lower alkyl group or an optionally substituted phenyl group.) Means the following halides or sulfates:

The optically active phenylethanol derivative in which s is 0 in the general formula (I) is an optically active alcohol (II)
Is reacted with an alkylating agent (IV).

This reaction is usually carried out in the presence of a basic substance. Examples of the basic substance include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metals such as lithium, sodium and potassium, sodium ethylate, and the like. Examples thereof include alkali metal alcoholates such as sodium methylate, alkali metal carbonates such as sodium carbonate and potassium carbonate, butyl lithium and the like.

Such a basic substance is required in an amount of at least 1 equivalent to the optically active alcohol, and the upper limit is not particularly limited, but is preferably in the range of 1 to 5 equivalents.

The alkylating agent used in this reaction is a halogen such as chloride, bromide, iodine or the like having an alkyl group or an alkoxyalkyl group which may be substituted by a halogen atom having 1 to 20 carbon atoms as exemplified below. Or sulfates (methanesulfonate, ethanesulfonate, benzenesulfonate,
Toluene sulfonic acid ester).

Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxy Butyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, Propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhex , Propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxyethyl , Pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl,
Hexylhexylpentyl, hexyloxyhexyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxymethyl, octyloxyethyl, octyl Oxypropyl,
Decyloxymethyl, decyloxyethyl, deloxypropyl, 1-methylethyl, 1-methylpropyl,
-Methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 2-
Methylethyl, 2-methylbutyl, 2,3-dimethylbutyl, 2,3,3-trimethylbutyl, 2-methylpentyl,
3-methylpentyl, 2,3-dimerpentyl, 2,4-dimethylpentyl, 2,3,3,4-tetramethylpentyl, 2-
Methylhexyl, 3-methylhexyl, 4-methylhexyl, 2,5-dimethylhexyl, 2-methylheptyl,
2-methyloctyl, 2-trihalomethylpentyl, 2
-Trihalomethylhexyl, 2-trihalomethylheptyl, 2-haloethyl, 2-halopropyl, 3-halopropyl, 3-halo-2-methylpropyl, 2,3-dihalopropyl, 2-halobutyl, 3-halobutyl, 4- Halobutyl, 2,3-dihalobutyl, 2,4-dihalobutyl, 3,4-
Dihalobutyl, 2-halo-3-methylbutyl, 2-halo-3,3-dimethylbutyl, 2-halopentyl, 3-halopentyl, 4-halopentyl, 5-halopentyl, 2,4
-Dihalopentyl, 2,5-dihalopentyl, 2-halo-
3-methylpentyl, 2-halo-4-methylpentyl,
2-halo-3-monohalomethyl-4-methylpentyl,
2-halohexyl, 3-halohexyl, 4-halohexyl, 5-halohexyl, 6-halohexyl, 2-haloheptyl, 2-halooctyl (however, halo in the above alkyl group means fluorine, chlorine, bromine or iodine; Is preferably fluorine or chlorine.) The alkyl group or alkoxyalkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom may be an optically active group.

The halides or sulfates having these optically active groups are derived from the corresponding alcohols, and some of the optically active alcohols can be easily prepared by the asymmetric metal catalyst of the corresponding ketone, asymmetric reduction by microorganisms or enzymes. Is obtained. Others can be derived from the following optically active amino acids and optically active oxyacids that are naturally occurring or obtained by resolution.

Valine, leucine, isoleucine, phenylalanine, threonine, alosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, aspartic acid, glutamic acid, mandelic acid, tropha Acid, 3-hydroxybutyric acid, malic acid, tartaric acid, isopropylmalic acid and the like.

The amount of the alkylating agent (IV) to be used is not less than 1 equivalent to the optically active alcohol (II), but is usually in the range of 1 to 5 equivalents.

As the reaction solvent, polar solvents such as dimethylsulfoxide, hesamethylphosphorylamide, N-methylpyrrolidone and the like can be used in addition to the solvents exemplified above.

The reaction temperature is usually −50 ° C. to 120 ° C., preferably −30 ° C.
It is in the range of ~ 100 ° C.

After completion of the reaction, usual separation means such as extraction, liquid separation,
By an operation such as concentration, an optically active phenylethanol derivative represented by the general formula (I) (where s = 0) can be obtained in good yield, which may be purified by column chromatography, recrystallization, etc., if necessary. can do.

In the alkylation reaction, when the substituent X of the alkylating agent represented by the general formula (IV) is an iodine atom, silver oxide can be used in place of the basic substance. .

In this case, the silver oxide is required to be at least 1 equivalent times the optically active alcohol (II), and the upper limit is not particularly limited, but is preferably 2 to 5 equivalent times.

The amount of the alkylating agent to be used is not less than 1 equivalent times the amount of the optically active alcohol (II).
The range is 10 equivalent times.

As the reaction solvent, the above-mentioned alkylating agent can be used as a solvent.In addition, for example, for the reaction of ethers such as tetrahydrofuran, ethyl ether, dioxane, acetone, methyl ethyl ketone, benzene, toluene and hexane, ketones, hydrocarbon solvents and the like. One or a mixture of inert solvents may be used.

The reaction temperature is usually 0 to 150 ° C, preferably 20 to 100 ° C.
Range.

 The reaction time is usually 1 hour to 7 days.

After the completion of the reaction, the silver salt is removed by filtration, and then subjected to general separation means, for example, extraction, liquid separation, concentration, column chromatography, distillation, etc., to obtain the compound represented by the general formula (I).
An optically active phenylethanol derivative represented by the following formula (where s = 0) can be obtained.

Examples of the optically active phenylethanol derivative represented by the general formula (I) thus obtained include the following.

In the compound name, alkyl (having 3 to 20 carbon atoms) is
An alkyl group having 3 to 20 carbon atoms is replaced with an alkyl (1 to 20 carbon atoms)
) Represents an alkyl group or an alkoxyalkyl group which may be substituted by a halogen atom having 1 to 20 carbon atoms, and specific examples thereof include those described above.

4-alkyl (3-20 carbon atoms) carbonyloxyphenyl 4- {1-alkyl (1-20 carbon atoms) oxyethyl} benzoate, 4-alkyl (3-20 carbon atoms) oxycarbonylphenyl 4- {1-alkyl (C1-20) oxyethyl} benzoic acid ester, 4-alkyl (C3-20) carbonyloxyphenyl 4- {1-alkyl (C1-20) carbonyloxyethyl} Benzoic acid ester, 4-alkyl (C3-20) oxycarbonylphenyl 4- {1-alkyl (C1-20) carbonyloxyethyl} benzoic acid ester, 4-alkyl (C3-20 carbon) ) Carbonyloxybenzoic acid 4- {1-alkyl (1-20 carbon atoms) oxyethyl} phenyl ester, 4-alkyl (3-20 carbon atoms) oxy 4- {1-alkyl (1 to 20 carbon atoms) oxyethyl} phenyl ester, 4-alkyl (3 to 20 carbon atoms) carbonyloxybenzoic acid 4- {1-alkyl (1 to 20 carbon atoms) ) Carbonyloxyethyl phenyl ester, 4-alkyl (3 to 20 carbon atoms) oxycarbonylphenyl 4- {1-alkyl (1 to 20 carbon atoms) carbonyloxyethyl phenyl ester, 4-alkyl (3 carbon atoms) ~ 20) carbonyloxy-
4'-biphenylyl 4- {1-alkyl (having 1 to 1 carbon atoms)
20) oxyethyl dibenzoate, 4-alkyl (3-20 carbon atoms) oxycarbonyl-
4'-biphenylyl 4- {1-alkyl (having 1 to 1 carbon atoms)
20) oxyethyl dibenzoate, 4-alkyl (3-20 carbon) carbonyloxy-
4'-biphenylyl 4- {1-alkyl (having 1 to 1 carbon atoms)
20) carbonyloxyethyl benzoate, 4-alkyl (3-20 carbon atoms) oxycarbonyl-
4'-biphenylyl 4- {1-alkyl (having 1 to 1 carbon atoms)
20) carbonyloxyethyl benzoate, 4-alkyl (3-20 carbon) carbonyloxy-
4-biphenylcarboxylic acid 4- {1-alkyl (C 1-20) oxyethyl} phenyl ester, 4-alkyl (C 3-20) oxycarbonyl-
4'-biphenylcarboxylic acid 4- {1-alkyl (1-20 carbon) oxyethyl} phenyl ester, 4-alkyl (3-20 carbon) carbonyloxy-
4'-biphenylcarboxylic acid 4- {1-alkyl (1 to 20 carbon atoms) carbonyloxyethyl} phenyl ester, 4-alkyl (3 to 20 carbon atoms) oxycarbonyl-
4'-biphenylcarboxylic acid 4- {1-alkyl (1 to 20 carbon atoms) carbonyloxyethyl} phenyl ester, 4-alkyl (3 to 20 carbon atoms) carbonyloxyphenyl 4- {1-alkyl (carbon number 1-20) oxyethyl {-4'-biphenylcarboxylic acid ester, 4-alkyl (3-20 carbon atoms) oxycarbonylphenyl 4- {1-alkyl (1-20 carbon) oxyethyl} -4'- Biphenylcarboxylic acid ester, 4-alkyl (C3-20) carbonyloxyphenyl 4- {1-alkyl (C1-20) carbonyloxyethyl} -4'-biphenylcarboxylic acid ester, 4-alkyl ( Oxycarbonylphenyl 4- {1-alkyl (C1-20) carbonyloxyethyl} -4'-biph 4-alkyl (having 3 to 20 carbon atoms) 4- {1-alkyl (having 1 to 20 carbon atoms) oxyethyl} -4'-biphenylyl ester, 4-alkyl (having 3 to 20 carbon atoms) 4-alkyl (having 3 carbon atoms) 4- {1-alkyl (1-20 carbon) oxyethyl} -4'-biphenylyl ester, 4-alkyl (3-20 carbon) carbonyloxybenzoic acid 4- { 1-alkyl (1-20 carbon atoms) carbonyloxyethyl -4'-biphenylyl ester, 4-alkyl (3-20 carbon atoms) oxycarbonylbenzoic acid 4- {1-alkyl (1-20 carbon atoms) Carbonyloxyethyl} -4'-biphenylyl ester, 4-alkyl (C3-20) carbonyloxy-
4 '-{1-alkyl (C1-20) oxyethyl} biphenyl, 4-alkyl (C3-20) carbonyloxy-
4 '-{1-alkyl (C1-20) carbonyloxyethyl} biphenyl.

In the present invention, the liquid crystal composition contains at least one optically active phenylethanol derivative represented by the above general formula (I) as a compounding component.

In this case, 0.1 to 99.9 of the liquid crystal composition from which the optically active phenylethanol derivative represented by the general formula (I) can be obtained.
% By weight, particularly preferably 1 to 99% by weight.

Further, by using such a liquid crystal composition, a liquid crystal element, for example, an optical switching element can be effectively used. In this case, a method of using the liquid crystal composition is not particularly limited, and a conventionally known method can be applied as it is. .

<Effect of the Invention> Thus, according to the present invention, a novel optically active phenylethanol derivative represented by the general formula (I) can be easily obtained at a high yield, and the compound is very excellent as a liquid crystal compound. Since it has characteristics, it can be effectively used as a liquid crystal composition and further as a liquid crystal element using the same.

<Example> Example 1 (+)-4-octylcarbonyloxy-4 '-(1
1.77 g (5 mmol) of -hydroxyethyl) biphenyl
Was dissolved in a mixture of 20 ml of anhydrous dimethylformamide and 10 ml of tetrahydrofuran, and 0.24% of 60% sodium hydride was dissolved.
g (6 mmol) are added. After stirring at 20-25 ° C for 1 hour, 1.54 g of hexyl p-toluenesulfonate
(6 mmol) and reacted at 30-35 ° C. for 2 hours.
After the completion of the reaction, the mixture is poured into 200 ml of water and extracted with 200 ml of toluene. The organic layer is thoroughly washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography (eluent: toluene) to give (+)-4-octylcarbonyloxy-4 '-(1-hexyloxyethyl) biphenyl
1.43 g (65% yield) was obtained.

Example 2 A reaction and a post-treatment were carried out in the same manner as in Example 1 except that 1.87 g (6 mmol) of p-toluenesulfonic acid octyl ester was used instead of p-toluenesulfonic acid hexyl ester. -1 was obtained.

Example 3 (+)-4- (1-hydroxyethyl) benzoic acid 4-
1.99 g (5 mmol) of octylcarbonylphenyl ester, 10.6 g (50 mmol) of 1-iodohexane, 4.6 g (20 mmol) of silver oxide and 5 ml of tetrohydrofuran were added, and the mixture was stirred at 40 to 50 ° C for 4 days. After completion of the reaction, 100 ml of toluene was added and the mixture was filtered, and the solution was concentrated under reduced pressure.
The obtained residue was separated and purified by silica gel column chromatography (eluent; toluene: ethyl acetate).
(+)-4- (1-hexyloxyethyl) benzoic acid 4
1.01 g of octylcarbonylphenyl ester (yield 42
%).

Examples 4 and 5 The same reaction and post-treatment were carried out as in Example 3 except that the substrates and reagents used were changed to the compounds shown in Table 1, and the results shown in Table 1 were obtained.

Example 6 4-(-)-4- (1-hydroxyethyl) benzoic acid 4-
2.20 g of undecylcarbonyloxyphenyl ester
(5 mmol) is dissolved in 20 ml of pyridine and 0.81 g (6 mmol) of hexanoyl chloride are added. 4 at 40-45 ° C
After reacting for hours, pour into 200 ml of water, and add
Then, the mixture was extracted with 200 ml of toluene and separated. The organic layer is washed with water, 5% aqueous sodium hydrogen carbonate and water in that order, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography (eluent; toluene: ethyl acetate),
(-)-4- (1-Hexanoyloxyethyl) benzoic acid 4-undecylcarbonyloxyphenyl ester 2.
51 g (93% yield) were obtained.

Example 7 In Example 6, (+)-4- (1-hydroxyethyl) -4'- was used instead of (-)-4- (1-hydroxyethyl) benzoic acid 4-undecylcarbonyloxyphenyl ester. 2.58 g (5 mmol) of biphenylcarboxylic acid 4-undecylcarbonyloxyphenyl ester
The reaction and post-treatment were carried out in the same manner as in Example 6 except for changing to the above, to obtain the results shown in Table 1.

Example 8 (+)-4- (1-hydroxyethyl) benzoic acid 4-
2.20 g of undecylcarbonyloxyphenyl ester
(5 mmol) and 0.90 g (6 mmol) of (2S) -chloro- (3S) -methylpentanoic acid were added to 207 ml of anhydrous dichloromethane.
Dissolved in N, N'-dicyclohexylcarbodiimide 1.2
2 g (6 mmol) and 0.1 g of 4-pyrrolidinopyridine are added and stirred at room temperature for 24 hours. After completion of the reaction, the precipitate is separated and 200 ml of toluene is added. The organic layer is washed with water, 5% acetic acid aqueous solution, 5% aqueous sodium bicarbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (eluent;
(Toluene: ethyl acetate) to give (+)-4-1-
2.46 g (86% yield) of ((2S) -chloro- (3S) -methylpentanoyloxyethyl) benzoic acid 4-undecylcarbonyloxyphenyl ester were obtained.

Example 9 A reaction and work-up were conducted in the same manner as in Example 8 except that 0.54 g (6 mmol) of methoxyacetic acid was used instead of (2S) -chloro- (3S) -methylpentanoic acid. The results shown in Table 1 were obtained.

Examples 10 and 11 The reaction and post-treatment were carried out in the same manner as in Example 8 except that the optically active alcohols shown in Table 1 were used as raw materials and the carboxylic acids (III) used were those shown in Table 1. The results shown in Table 1 were obtained.

Examples 12 to 16 The reaction and post-treatment were carried out in the same manner as in Example 1 except that the optically active alcohols shown in Table 1 were used as raw materials, and that the alkylating agent (IV) shown in Table 1 was used. The results shown in Table 1 were obtained.

Example 17 The two liquid crystal compounds were mixed while being heated and melted at a predetermined weight ratio to prepare a liquid crystal composition.

The obtained liquid crystal composition showed a chiral smectic C phase (Sc ^* ) at 39 ° C. or lower, and the spontaneous polarization at 29 ° C. was 6 nC / cm ² .

The above-mentioned known compound showed a Sc ^* phase at 70 ° C. or lower, and spontaneous polarization was almost 0 nC / cm ² .

(Liquid crystal element manufacturing method)

A polyimide-based polymer film is provided on a glass substrate on which an indium oxide transparent electrode is provided, and wrapped using gauze in a certain direction, and glass fibers (diameter 6 μm) are set so that the lapping directions of the two substrates are parallel. Is used as a spacer to assemble a liquid crystal cell, and the liquid crystal composition is vacuum-sealed into the liquid crystal cell to obtain a liquid crystal element.

This liquid crystal element is placed between two orthogonal polarizers,
When an electric field was applied, a change in transmitted light intensity was observed by applying 20V.

The response time is calculated from the change in transmitted light intensity at this time.
The value was 0.5 ms, and the contrast was 1:10.

Example 18 A liquid crystal composition was prepared in the same manner as in Example 17, except that the compound of Example 1 was replaced with the optically active phenylethanol derivative of the present invention, which did not show a Sc ^* phase. The spontaneous polarization was measured for each. Table 2 shows the results.

As a result, these compounds of the present invention are themselves Sc ^*
Does not show that it is effective in expanding spontaneous polarization by blending with a known compound.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 19/20 C09K 19/20 19/46 19/46 G02F 1/13 500 G02F 1/13 500 (72) Inventor Koichi Fujisawa Ibaraki No. 6, Kitahara, Tsukuba, Japan Sumitomo Chemical Co., Ltd. (56) References JP-A-62-583 (JP, A) JP-A-64-56647 (JP, A) Patent 2512983 (JP, B2) −32657 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 69/773 C07C 69/90 C07C 69/82 C07C 69/78 C07C 69/94 C09K 19/20 C09K 19 / 46 G02F 1/13 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (9)

(57) [Claims] (1) General formula (Wherein, R ₁ represents an alkyl group having 3 to 20 carbon atoms; R ₂ represents an alkyl group having 1 to 20 carbon atoms;
X represents an alkyl group having 20 or an alkoxyalkyl group having 2 to 20 carbon atoms, X represents -COO- or -OCO-, and Y represents-
Indicates COO- or -OCO-. p and l are each 1 or 2, and m and s are 0 or 1. However, when m is 0, 1 and p are not 2 at the same time, and Y is -COO-. And Y is -OCO- except when Y is -OCO-, m is 0, l is 1, p is 1 and s is 0.
Excluding the case where m is 0, l is 1, p is 1, s is 1, and R ₂ is an alkyl group. * Indicates that it is an asymmetric carbon atom. ) An optically active phenylethanol derivative represented by the formula: 2. The optically active phenylethanol derivative according to claim 1, wherein s is 0. 3. The optically active phenylethanol derivative according to claim 1, wherein s is 1. 4. The optically active phenylethanol derivative according to claim 1, wherein X is —COO—. 5. The optically active phenylethanol derivative according to claim 1, wherein X is -OCO-. 6. The general formula (Wherein, R ₁ represents an alkyl group having 3 to 20 carbon atoms, and X represents-
Y represents -COO- or -OCO-;
Is shown. p and l are each 1 or 2, and m and s are 0 or 1. However, when m is 0, l and p
Are not simultaneously 2 and Y is -COO-. *
The mark indicates an asymmetric carbon atom. ) And an optically active alcohol represented by the general formula (Wherein, R ₂ represents an alkyl group having 1 to 20 carbon atoms, a halogen atom-substituted alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and R ′ represents a hydroxyl group or a halogen atom. 4. The method for producing an optically active phenylethanol derivative according to claim 3, wherein the carboxylic acid represented by the following formula is reacted. 7. The general formula (Wherein, R ₁ represents an alkyl group having 3 to 20 carbon atoms, and X represents-
Y represents -COO- or -OCO-;
Is shown. p and l are each 1 or 2, and m and s are 0 or 1. However, when m is 0, l and p
Are not simultaneously 2 and Y is -COO-. *
The mark indicates an asymmetric carbon atom. ) And an optically active alcohol acid represented by the general formula X'-R ₂ (wherein, R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkyl group or a carbon number of 2 to the halogen atom-substituted having 1 to 20 carbon atoms And X 'represents a halogen atom or
Indicates OSO ₂ R. Here, R represents a lower alkyl group, a phenyl group or a tolyl group. 3. The method for producing an optically active phenylethanol derivative according to claim 2, wherein the alkylating agent represented by the formula is condensed. 8. A liquid crystal composition comprising the optically active phenylethanol derivative according to claim 1 as at least one compounding component. 9. A liquid crystal device comprising a liquid crystal composition containing at least one optically active phenylethanol derivative according to claim 1 as a compounding component.