JP2797508B2 - Optically active heterocyclic compound, method for producing the same, liquid crystal composition containing the same as an active ingredient, and liquid crystal device using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an optically active heterocyclic compound, a method for producing the compound, a liquid crystal composition containing the compound as an active ingredient, and a liquid crystal device using the same.

<Prior Art> Ferroelectric liquid crystal has been proposed for use as a liquid crystal device by Clark and Lagerwall (JP-A-56-107216, U.S. Pat. No. 4367924, etc.). ).

The ferroelectric liquid crystal has an optically active group in a molecule and has spontaneous polarization, so that it can exhibit high-speed response and memory properties, and thus is suitable for a display with a high-definition large screen.

In general, it is said that the speed of high-speed response, which is a characteristic of ferroelectric liquid crystals, is correlated with the magnitude of spontaneous polarization, and it is considered that spontaneous polarization should be increased in order to increase the speed. .

Therefore, a polar group has been introduced into the molecule.However, most of the conventional ferroelectric liquid crystal compounds have a polar group with a small polarity or cannot effectively introduce the polar group into the molecule. there were.

Further, in the ferroelectric liquid crystal, its manifestation temperature range is also an important factor.
That is, it is necessary to keep the temperature near room temperature.

However, the development of a ferroelectric liquid crystal that is excellent in high-speed response and exhibits a liquid crystal phase near room temperature has not yet been sufficiently developed.
Moreover, there are very few ferroelectric liquid crystal compounds having an asymmetric carbon atom directly bonded to the core (phenyl or biphenyl group).

<Problems to be Solved by the Invention> An object of the present invention is to provide a ferroelectric liquid crystal material having excellent spontaneous polarization, capable of high-speed response, and exhibiting liquid crystallinity in a lower temperature range. I do.

<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 by a halogen atom having 1 to 20 carbon atoms, and X represents-
Represents COO- or -OCO-, Y represents -O-, -COO- or -OCO-, and Ar represents a formula Represents a group represented by l represents 1 or 2, q represents an integer of 0 to 5, m and s each represent 0 or 1, and * represents an asymmetric carbon atom. Provided that R ² is an alkyl group, X is —OCO—, l is 1, m,
q and s are 0, and Ar is Except in the case of ), A method for producing the compound, a liquid crystal composition containing the compound as an active ingredient, and a liquid crystal device using the compound.

 Hereinafter, the present invention will be described in detail.

(1) In the general formula (I), the heterocyclic compound (I) wherein X is -OCO- is a compound represented by the general formula (II) R _1- (Y) _m -Ar-OH (II) (wherein R ₁ , Y , Ar and m have the same meanings as described above) and an alcohol represented by the general formula (III): (Wherein, R ₂ , l, q, s and * have the same meanings as described above, and R ′ represents a hydroxyl group or a halogen atom.) Can be.

(2) Next, in the general formula (I), the heterocyclic compound (I) in which X is -COO- is a compound represented by the general formula (IV) R _1- (Y) _m -Ar-COR '(IV) , R ₁ , Y, Ar, R ′ and m have the same meanings as described above) and a carboxylic acid represented by the general formula (V): (Wherein, R ₂ , l, q, s and * have the same meanings as described above).

For the reaction between the alcohols (II) and the optically active carboxylic acids (III) in the production method of the above (I), a usual esterification method can be applied, and in the presence or absence of a solvent, a catalyst is used. The reaction can be carried out by using

When a solvent is used in the above reaction, examples of the solvent include aliphatic solvents such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane and pyridine. Or aromatic hydrocarbons,
Solvents inert to the reaction, such as ethers, ketones, and halogenated hydrocarbons, and mixtures thereof. The amount can be used without any particular limitation.

In the above reaction, the amount of the reaction reagent used can be arbitrarily determined, but in order to effectively use the optically active carboxylic acid (III), it is preferable to carry out the reaction using an excess amount of the alcohol (II) as a partner raw material. Usually, 1 to 4 equivalents, preferably 1 to 2 equivalents are used.

If necessary, a catalyst can be used in the above reaction,
Examples of the catalyst used include organic or inorganic basic substances such as dimethylaminopyridine, triethylamine, tri-n-butylamine, pyridine, picoline, lysine, imidazole, sodium carbonate, sodium methylate, and potassium hydrogen carbonate.

Further, an organic acid or an inorganic acid such as toluenesulfonic acid, methanesulfonic acid, or sulfuric acid can be used as a catalyst.

The amount of the catalyst used varies depending on the type of each reaction raw material used and the combination of the catalyst used, etc., and cannot always be specified. For example, when an acid halide is used, the amount of the basic compound is at least one equivalent of the acid halide. The substance is used.

Further, when the optically active carboxylic acid represented by the general formula (III) is an optically active carboxylic acid, N, N'-dicyclohexylcarbodiimide, N-cyclohexyl-
Carbodiimides such as N '-(4-diethylamino) cyclohexylcarbodiimide are preferably used as a condensing agent, and if necessary, 4-pyrrolidinopyridine, pyridine,
An organic base such as triethylamine can be used in combination.

The amount of the condensing agent used in this case is usually 1 to 1.2 equivalent times based on the optically active carboxylic acid, and when an organic base is used in combination, the amount of the organic base used is 0.01 to 0.2 equivalent times based on the condensing agent. .

The above alcohols (II) and optically active carboxylic acids (II
The reaction temperature in the reaction with I) is usually -30C to 100C, preferably -25C to 80C.

 The reaction time is not particularly limited.

After completion of the reaction, usual separation means such as extraction, liquid separation,
The desired general formula (I) is obtained from the reaction mixture by concentration or the like.
An optically active heterocyclic compound represented by (X = -OCO-) can be isolated and, if necessary, purified by column chromatography, recrystallization, or the like.

The above-mentioned alcohols (II), which are raw material compounds, are mostly known compounds and can be produced according to the method described in the literature.

Such alcohols (II) include 5-substituted-2-
(4-hydroxyphenyl) pyrimidine, 2-substituted-5
-(4-hydroxyphenyl) pyrimidine, 2- (4-
Substituted phenyl) -5-hydroxypyrimidine, 5- (4
-Substituted phenyl) -2-hydroxypyrimidine, 2-substituted-5-hydroxypyrimidine, 5-substituted-2-hydroxypyrimidine, and these can also be used as metal phenolates. In the compound names, “substituted” represents an alkyl, alkoxy, alkylcarbonyloxy, or alkyloxycarbonyl group.

Here, each of the above alkyls or alkoxys has a linear alkyl group having 3 to 20 carbon atoms,
The following are specific examples of the alkyl group.

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

These alcohols can be reacted with the optically active carboxylic acids (III) as metal alcoholates.

The other material, optically active carboxylic acids (III),
Although it is a novel compound, it can be produced, for example, by the following method.

When q = 1-5, s = 0 (Wherein, R ₂ and l have the same meanings as described above, R ″ represents a lower alkyl group, T represents a halogen atom, an arylsulfonyloxy group, etc.) When q = 1 to 5, s = 1 (Wherein, R ₂ , T and l have the same meanings as described above;
Represents a benzyl group, a t-butyldimethylsilyl group, a tetrahydropyranyl group or the like. ) When q = 0 (In the formula, R ″, R ₂ , l and s have the same meanings as described above, and Z ′ represents a hydrogen atom, a lower alkyl group or an optionally substituted benzyl group.) These optically active carboxylic acids Contains an acid halide (eg, acid chloride, acid bromide).

Specific examples of the substituent R ₂ in the general formula (III) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and heptadecyl. Octadecyl, nonadecyl, eicosyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxy Pentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, propoxymethyl, propoxyethyl, propoxypropyl, Poxybutyl, propoxypentyl, propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxynonyl 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, 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 and 2-halooctyl (however, halo in the above alkyl group represents fluorine, chlorine, bromine or iodine).

Furthermore, when s = 1, in addition to the above, examples include halomethyl, 1-haloethyl, 1-halopropyl, 1-halobutyl, 1-halopentyl, 1-halooctyl, and the like.

Incidentally, the alkyl group or the alkoxyalkyl group which may be substituted with a halogen atom may be an optically active group.

The reaction between the carboxylic acids (IV) and the optically active phenols (V) in the production method (2) can be carried out in the same manner as in the above-mentioned synthesis method of the general formula (I) (X = —OCO—). it can.

However, in order to effectively use the optically active phenols (V), the carboxylic acids (IV), which are their counterparts, are used.
The reaction is preferably carried out using an excess amount of
It is used up to 4 equivalents, preferably 1 to 2 equivalents.

Further, when the carboxylic acid represented by the general formula (IV) is a carboxylic acid, carbodiimide is preferably used as a condensing agent, as in the case of the general formula (I) (X = —OCO—). Can be similarly implemented.

The reaction temperature of the reaction between the carboxylic acids (IV) and the optically active phenols (V) is usually from -30 ° C to 10 ° C.
0 ° C., preferably -25 ° C. to 80 ° C.

 The reaction time is not particularly limited.

After completion of the reaction, the desired optically active heterocyclic compound represented by the general formula (I) (X = —COO—) is isolated from the reaction mixture by a conventional separation means, for example, extraction, liquid separation, concentration, and the like. It can be purified by column chromatography, recrystallization or the like, if necessary.

Many of the carboxylic acids (IV) as raw materials are known compounds, and can be produced according to the method described in the literature.

As such carboxylic acids (IV), 5-substituted-
2- (4-carboxyphenyl) pyrimidine, 2-substituted-5- (4-carboxyphenyl) pyrimidine, 2-
(4-substituted phenyl) -5-pyrimidinecarboxylic acid, 5
-(4-substituted phenyl) -2-pyrimidinecarboxylic acid,
2-substituted-5-pyrimidinecarboxylic acid, 5-substituted-2-
Pyrimidine carboxylic acids are mentioned, and these carboxylic acids are also used as acid halides, that is, acid chlorides, acid bromides, and the like. In the compound names, "substituted" indicates an alkyl, alkoxy, alkylcarbonyloxy, or alkyloxycarbonyl group.

Here, as the alkyl forming the above alkyl or alkoxy, specifically, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl and the like can be mentioned.

The optically active phenol (V), which is the other raw material, can be produced as follows.

(In the formula, R ₂ , l, q, s, and * represent the same meaning as described above.) The starting materials in the above reaction formula can be produced by the above-described method.

Examples of the substituent R ₂ include those exemplified as R ₂ in the formula (III).

Specific examples of the optically active heterocyclic compound (I) obtained by the production methods (1) and (2) include the following. However, in the compound name, alkyl (having 3 to 20 carbon atoms) may be substituted with an alkyl group having 3 to 20 carbon atoms, and alkyl (having 1 to 20 carbon atoms) may be substituted with a halogen atom having 1 to 20 carbon atoms. Represents a good alkyl group or an alkoxyalkyl group, and the term "heterocycle" refers to 4 ', 5-disubstituted-2-phenylpyrimidine 4 ', 2-disubstituted-5-phenylpyrimidine 2,5-disubstituted-pyrimidine Represents a 2-substituted heterocycle.

4- {alkyl (3-20 carbon atoms) heterocyclic oxycarbonyl} -1- {1-alkyl (1-20 carbon atoms) oxyethyl} benzene, 4- {alkyl (3-20 carbon atoms)
Oxyheterocyclic oxycarbonyl {-1-} 1-alkyl (1-20 carbon atoms) oxyethyl {benzene, 4- {alkyl (3-20 carbon atoms) carbonyloxyheterocyclic oxycarbonyl} -1- {1- Alkyl (1-20 carbon atoms)
Oxyethyl} benzene, 4- {alkyl (C3-20) oxycarbonylheterocyclicoxycarbonyl}
-1- {1-alkyl (1-20 carbon atoms) oxyethyl} benzene, 4- {alkyl (3-20 carbon atoms) heterocyclic oxycarbonyl-1- {1-alkyl (1 carbon atoms)
20) carbonyloxyethyl {benzene, 4- {alkyl (C3-20) oxyheterocyclic oxycarbonyl} -1- {1-alkyl (C1-20) carbonyloxyethyl} benzene, 4- ｛Alkyl (C3
-20) carbonyloxyheterocyclicoxycarbonyl｝-
1- {1-alkyl (C1-C20) carbonyloxyethyl} benzene, 4- {alkyl (C3-C20)
Oxycarbonylheterocycleoxycarbonyl} -1-
{1-alkyl (C1-20) carbonyloxyethyl} benzene, 4- {alkyl (C3-20) heterocyclic carbonyloxy} -1- {1-alkyl (C1-20) Oxyethyl {benzene, 4- {alkyl (3-20 carbon) oxyheterocyclic carbonyloxy}-
1- {1-alkyl (C1-20) oxyethyl}
Benzene, 4- {alkyl (3 to 20 carbon atoms) carbonyloxy heterocyclic carbonyloxy} -1- {1-alkyl (1 to 20 carbon atoms) oxyethyl} benzene, 4- {alkyl (3 to 20 carbon atoms) Oxycarbonylheterocyclic carbonyloxy} -1- {1-alkyl (C1-20) oxyethyl} benzene, 4- {alkyl (C3-20) heterocyclic carbonyloxy} -1- {1} -Alkyl (having 1 to 20 carbon atoms) carbonyloxyethyl {benzene, 4- {alkyl (having 3 to 20 carbon atoms) oxyheterocyclic carbonyloxy} -1- {1-alkyl (having 1 to 20 carbon atoms)
Carbonyloxyethyl {benzene, 4- {alkyl (3 to 20 carbon atoms) carbonyloxy heterocyclic carbonyloxy} -1- {1-alkyl (1 to 20 carbon atoms) carbonyloxyethyl} benzene, 4- {alkyl Oxycarbonyl heterocyclic carbonyloxy {1- {1-alkyl (C1-20) carbonyloxyethyl} benzene (4-C20) 4- (alkyl) C3-C20 heterocyclic (3-20 carbon) Oxycarbonyl {-4 '-{1-alkyl (C1-20) oxyethyl} biphenyl, 4- {alkyl (C3-20) oxyheterocyclic oxycarbonyl {-4'-{1-alkyl ( 1-20 carbon atoms
Oxyethyl} biphenyl, 4- {alkyl (3-20 carbon) carbonyloxyheterocycleoxycarbonyl} -4 ′-{1-alkyl (1-20 carbon) oxyethyl} biphenyl, 4- {alkyl ( C3-C20 oxycarbonylheterocycleoxycarbonyl {-4 '-{1-alkyl (C1-C20) oxyethyl} biphenyl, 4- {alkyl (C3-C20) heterocycleoxycarbonyl {-4 '-{1-alkyl (C1-20) carbonyloxyethyl} biphenyl, 4- {alkyl (C3-20) oxyheterocyclicoxycarbonyl} -4'-{1-alkyl ( 1-20 carbon atoms
Carbonyloxyethyl} biphenyl, 4- {alkyl (C3-20) carbonyloxyheterocyclicoxycarbonyl} -4 '-{1-alkyl (C1-20) carbonyloxyethyl} biphenyl, 4 -{Alkyl (3-20 carbon atoms) oxycarbonylheterocycleoxycarbonyl} -4 '-{1-alkyl (1-20 carbon atoms) carbonyloxyethyl} biphenyl, 4- {alkyl (3-20 carbon atoms) ) -Heterocyclic carbonyloxy {-4 '-{1-alkyl (C1-20) oxyethyl} biphenyl, 4- {alkyl (C3-20) oxyheterocyclic carbonyloxy) -4'-} 1-alkyl (C 1-20
Oxyethyl} biphenyl, 4- {alkyl (C 3-20) carbonyloxyheterocyclic carbonyloxy} -4 ′-{1-alkyl (C 3-20) oxyethyl} biphenyl, 4- {alkyl ( C3-C20 oxycarbonylheterocyclic carbonyloxy {-4 '-{1-alkyl (C1-C20) oxyethyl} biphenyl, 4- {alkyl (C3-C20) heterocyclic carbonyloxy {-4 '-{1-alkyl (C1-20) carbonyloxyethyl} biphenyl, 4- {alkyl (C3-20) oxyheterocyclecarbonyloxy) -4'-{1-alkyl ( 1-20 carbon atoms
Carbonyloxyethyl} biphenyl, 4- {alkyl (C3-20) carbonyloxyheterocyclic carbonyloxy} -4 '-{1-alkyl (C3-20) carbonyloxyethyl} biphenyl, 4 -{Alkyl (C3-20) oxycarbonylheterocyclic carbonyloxy} -4 '-{1-alkyl (C1-20) carbonyloxyethyl} biphenyl.

It also contains an optically active compound exemplified below and a substituent.

That is, the 2-alkyl (C 1-20) oxy (or carbonyloxy) ethyl group of the compound exemplified below is a 3-alkyl (C 1-20) oxy (or carbonyloxy) propyl, Alkyl (1-20 carbon) oxy (or carbonyloxy) butyl, 5-alkyl (1-20 carbon) oxy (or carbonyloxy) pentyl, and 6-alkyl (1-20 carbon) oxy ( Or carbonyloxy) hexyl.

4- {alkyl (C3-C20) heterocyclic oxycarbonyl} -1- {1-methyl-2-alkyl (C1-C2)
20) oxyethyl dibenzene, 4- {alkyl (C3-20) oxyheterocyclic oxycarbonyl} -1- {1-methyl-2-alkyl (C1-20) oxyethyl} benzene, 4- {Alkyl (3-20 carbon atoms) carbonyloxyheterocyclicoxycarbonyl} -1- {1-methyl-2-alkyl (1-20 carbon atoms) oxyethyl} benzene, 4- {alkyl (3-20 carbon atoms) Oxycarbonylheterocyclic oxycarbonyl} -1- {1-methyl-2-alkyl (C1-20) oxyethyl} benzene, 4- {alkyl (C3-20) heterocyclicoxycarbonyl}- 1- {1-methyl-2-alkyl (having 1 to 1 carbon atoms)
20) carbonyloxyethyl {benzene, 4- {alkyl (C3-20) oxyheterocyclic oxycarbonyl} -1- {1-methyl-2-alkyl (C1-20) carbonyloxyethyl} Benzene, 4- {alkyl (3-20 carbon atoms) carbonyloxyheterocycleoxycarbonyl} -1- {1-methyl-2-alkyl (1-20 carbon atoms) carbonyloxyethyl} benzene, 4- {alkyl Oxycarbonyl heterocyclic oxycarbonyl {1- {1-methyl-2-alkyl (C1-C20) carbonyloxyethyl} benzene (4-C20) 4-, alkyl (C3-C20) Heterocyclic oxycarbonyl} -4 ′-{1-methyl-2-alkyl (having 1 carbon atom)
-20) oxyethyl dibiphenyl, 4- {alkyl (3-20 carbon) oxyheterocyclic oxycarbonyl} -4 '-{1-methyl-2-alkyl (1-20 carbon) oxyethyl} biphenyl, 4- {alkyl (3-20 carbon atoms) carbonyloxyheterocyclicoxycarbonyl} -4 ′-{1-methyl-2-alkyl (1-20 carbon atoms) oxyethyl} biphenyl, 4- {alkyl (carbon number 3-20) oxycarbonylheterocycleoxycarbonyl {-4 '-{1-methyl-2-alkyl (C1-20) oxyethyl} biphenyl, 4- {alkyl (C3-20) heterocycle Oxycarbonyl {-4 '-} 1-methyl-2-alkyl (C 1
Carbonyloxyethyl} biphenyl, 4- {alkyl (3-20 carbon atoms) oxyheterocyclicoxycarbonyl} -4 ′-{1-methyl-2-alkyl (1-20 carbon atoms) carbonyloxy Ethyl {biphenyl, 4- {alkyl (C3-20) carbonyloxyheterocyclicoxycarbonyl} -4 '-{1-methyl-2-alkyl (C1-20) carbonyloxyethyl} biphenyl, 4 -{Alkyl (C 3-20) oxycarbonylheterocyclic oxycarbonyl} -4 ′-{1-methyl-2-alkyl (C 1-20) carbonyloxyethyl} biphenyl, 4- {alkyl (carbon Heterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (having 3 to 20 carbon atoms)
20) oxyethyl} benzene, 4- {alkyl (C3-20) oxyheterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (C1-20) oxyethyl} benzene, 4- {Alkyl (C3-20) carbonyloxyheterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (C1-20) oxyethyl} benzene, 4- {alkyl (C3-20) Oxycarbonylheterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (C1-20) oxyethyl} benzene, 4- {alkyl (C3-20) heterocyclic carbonyloxy}- 1- {1-methyl-2-alkyl (having 1 to 1 carbon atoms)
20) carbonyloxyethyl {benzene, 4- {alkyl (C3-20) oxyheterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (C1-20) carbonyloxyethyl} Benzene, 4- {alkyl (3 to 20 carbon atoms) carbonyloxy heterocyclic carbonyloxy} -1- {1-methyl-2-alkyl (1 to 20 carbon atoms) carbonyloxyethyl} benzene, 4- {alkyl Oxycarbonyl heterocyclic carbonyloxy {-1- {1-methyl-2-alkyl (C1-C20) carbonyloxyethyl} benzene (4-C20) 4-, alkyl (C3-C20) Heterocyclic carbonyloxy} -4 '-{1-methyl-2-alkyl (having 1 carbon atom)
-20-oxyethyl} biphenyl, 4- {alkyl (3-20 carbon) oxyheterocyclic carbonyloxy} -4 ′-{1-methyl-2-alkyl (1-20 carbon) oxyethyl} biphenyl, 4- {alkyl (3 to 20 carbon atoms) carbonyloxyheterocyclic carbonyloxy} -4 ′-{1-methyl-2-alkyl (1 to 20 carbon atoms) oxyethyl} biphenyl, 4- {alkyl (carbon number 3-20) oxycarbonylheterocyclecarbonyloxy {-4 '-{1-methyl-2-alkyl (C1-20) oxyethyl} biphenyl, 4- {alkyl (C3-20) heterocycle Carbonyloxy {-4 '-} 1-methyl-2-alkyl (C 1
Carbonyloxyethyl} biphenyl, 4- {alkyl (3-20 carbon) oxyheterocyclic carbonyloxy} -4 ′-{1-methyl-2-alkyl (1-20 carbon) carbonyloxy Ethyl {biphenyl, 4- {alkyl (3-20 carbon atoms) carbonyloxyheterocyclic carbonyloxy} -4 ′-{1-methyl-2-alkyl (1-20 carbon atoms) carbonyloxyethyl} biphenyl, 4 -{Alkyl (C3-20) oxycarbonylheterocyclic carbonyloxy} -4 '-{1-methyl-2-alkyl (C1-20) carbonyloxyethyl} biphenyl.

When the thus obtained optically active heterocyclic compound represented by the general formula (I) is used as a component of a liquid crystal, particularly a component of a ferroelectric liquid crystal, practical optical stability and the like are not improved. When considered, the substituent R ₂ is preferably alkyl or alkoxyalkyl.

Further, in order to exhibit a high-speed response characteristic of a ferroelectric liquid crystal, a liquid crystal compound preferably has a small viscosity coefficient. In the case of an optically active heterocyclic compound represented by the general formula (I), l = 1 is particularly preferred.

Further, when X = —COO— in the general formula (I), the phase sequence of the liquid crystal compound is as follows: Therefore, when used as a display element material, a birefringent method is preferable, and when X = —OCO—, the phase series is as follows: Or In this case, the GH type system is more preferably adopted.

In the present invention, the liquid crystal composition contains at least one optically active heterocyclic compound represented by the general formula (I) as a compounding component. In this case, the optically active heterocyclic compound represented by the general formula (I) is used in an amount of 0.1 to 99.9% by weight, particularly preferably 1 to 99% by weight of the obtained liquid crystal composition.
It is good to use it in the ratio which becomes 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> Since the optically active heterocyclic compound represented by the general formula (I) of the present invention has very excellent properties as a liquid crystal compound, it can be used as a liquid crystal composition and as a liquid crystal device using the same. It can be used effectively. Further, the heterocyclic compound (I) can be industrially effectively obtained by the production method of the present invention.

<Examples> Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not particularly limited thereto.

Example 1 1.97 g (6 mmol) of 2- (4-hydroxyphenyl) -5-decyloxypyrimidine and (+)-4- (1
-Hexyloxyethyl) benzoic acid (1.25 g, 5 mmol) was dissolved in anhydrous dichloromethane (20 ml), and N, N'-dicyclohexylcarbodiimide (1.22 g, 6 mmol) was added.
0.1 g of pyrrolidinopyridine was added, and the mixture was stirred at room temperature for one day. After completion of the reaction, the precipitate was separated, and toluene 200m
The mixture was washed with water, 5% acetic acid, water, 5% aqueous sodium bicarbonate and water in that order, and the organic layer was 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).
And purified by (+)-4- (1-hexyloxyethyl)
4- (5-decyloxy-2-pyrimidine) of benzoic acid
2.50 g (89% yield) of the phenyl ester was obtained.

Example 2 Acid chloride 1.41 derived from (+)-4- (1-hexyloxyethyl) benzoic acid by dissolving 1.97 g (6 mmol) of 2- (4-hydroxyphenyl) -5-decyloxypyrimidine in 20 ml of pyridine. g (5 mmol) was added and reacted at 30-40 ° C for 2 hours. After the completion of the reaction, water 20
0 ml, adjust the pH to 3-4 with hydrochloric acid, and then add 200 ml of toluene
And the organic layer is washed with water, 5% aqueous sodium bicarbonate and water in this order,
The organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluent; toluene-ethyl acetate) to give (+)-4- (1-hexyloxyethyl) benzoic acid 4- ( 2.76 g (96% yield) of 5-decyloxy-2-pyrimidine) phenyl ester were obtained.

Examples 3 to 21 The reaction and post-treatment were carried out in the same manner as in Example 1 except that the raw materials used in Example 1 were changed to those shown in Table 1, and the results were as shown in Table 1.

Table 2 shows phase transition points and spontaneous polarizations of typical compounds among the compounds obtained in the above Examples.

Examples 22 and 23 Using the liquid crystal compound, liquid crystal compositions shown in Table 3 were prepared. The preparation was carried out by mixing and weighing a predetermined compound at a predetermined weight while heating and melting it in a sample bottle.

(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 rubbing is performed using gauze in a certain direction, and glass fibers (diameter: 5 μm) are rubbed so that the rubbing directions of the two substrates are parallel. A liquid crystal cell was assembled as a spacer, and the above liquid crystal composition (compound) was vacuum-sealed to obtain a liquid crystal element.

This liquid crystal element was combined with a polarizer, an electric field of 20 V was applied, and a change in transmitted light intensity was observed. As a result, it became clear that the element became a switching element.

As is clear from the results, when the liquid crystal material of the present invention was used, the liquid crystal material of the present invention was compared with the comparative example. The temperature range could be lowered, and the spontaneous polarization could be increased.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07M 7:00 (72) Inventor Masayoshi Minami 3-1-1 98, Kasuganaka, Konohana-ku, Osaka City, Osaka Sumitomo Chemical Co., Ltd. ( 72) Inventor Takeshi Tani 6th Kitahara, Tsukuba City, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Chitsu Kawakami 6th Kitahara, Tsukuba City, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Koichi Fujisawa Tsukuba City, Ibaraki Prefecture No. 6 Kitahara Sumitomo Chemical Co., Ltd. (56) References JP-A-2-62848 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) CA (STN) CAOLD (STN) REGISTRY (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 or an alkoxyalkyl group optionally substituted by a halogen atom having 1 to 20 carbon atoms, and X represents-
Represents COO- or -OCO-, Y represents -O-, -COO- or -OCO-, and Ar represents a formula Represents a group represented by l represents 1 or 2, q represents an integer of 0 to 5, m and s each represent 0 or 1, and * represents an asymmetric carbon atom. Provided that R ² is an alkyl group, X is —OCO—, l is 1,
m, q, and s are 0, and Ar is Except in the case of ) An optically active heterocyclic compound represented by the formula: 2. The optically active heterocyclic compound according to claim 1, wherein s is 0. 3. The optically active heterocyclic compound according to claim 1, wherein s is 1. 4. The optically active heterocyclic compound according to claim 1, wherein X is —COO—. 5. The optically active heterocyclic compound according to claim 1, wherein X is -OCO-. 6. A compound represented by the general formula R _1- (Y) _m -Ar-OH (wherein R ₁ represents an alkyl group having 3 to 20 carbon atoms, and Y represents -O-, -COO- or -OCO-). And m represents 0 or 1, and Ar represents the formula Or Represents a group represented by ) And an alcohol represented by the general formula (Wherein, R ₂ represents an alkyl group or an alkoxyalkyl group which may be substituted with a halogen atom having 1 to 20 carbon atoms, R ′ represents a hydroxyl group or a halogen atom, 1 represents 1 or 2, q Represents an integer of 0 to 5, s represents 0 or 1, and * represents an asymmetric carbon atom.) An optically active carboxylic acid represented by the following formula: 6. The method for producing an optically active heterocyclic compound according to 5. 7. A compound of the general formula R _1- (Y) _m -Ar-COR ', wherein R ₁ represents an alkyl group having 3 to 20 carbon atoms;
Represents a hydroxyl group or a halogen atom, and Y represents -O-,-
Represents COO- or -OCO-, m represents 0 or 1, and Ar represents the formula Represents a group represented by ) And a carboxylic acid represented by the general formula (Wherein, R ₂ represents an alkyl group or an alkoxyalkyl group which may be substituted with a halogen atom having 1 to 20 carbon atoms, 1 represents 1 or 2, q represents an integer of 0 to 5, s Represents 0 or 1, and the symbol * represents an asymmetric carbon atom.) The optically active phenol represented by the formula is reacted to produce the optically active heterocyclic compound according to claim 4. Law. 8. A liquid crystal composition comprising the optically active heterocyclic compound according to claim 1 as at least one compounding component. 9. A liquid crystal device using the liquid crystal composition according to claim 8.