JP3038855B2 - Phenylpyrimidine derivative containing fluorine, method for producing the same, liquid crystal composition containing the same as an active ingredient, and liquid crystal element using the same - Google Patents

Description

The present invention relates to a phenylpyrimidine derivative useful as a compounding component of a ferroelectric liquid crystal or a composition thereof, a method for producing the same, a liquid crystal composition using the same as an active ingredient, and The present invention relates to a liquid crystal element 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 as the drive voltage and power consumption are lower. 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 insufficient. Although various improvements have been made as described above, a TN type display element having a high response speed has not been realized. However, in a new display system using a ferroelectric liquid crystal, which has been actively studied recently, there is a possibility that the response speed can be remarkably improved (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 the ferroelectric liquid crystal material used in the ferroelectric liquid crystal device 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.

In addition, not only ferroelectric liquid crystal compositions consisting only of ferroelectric liquid crystal compounds, but also JP-A-61-195187 discloses non-chiral smectic C, F, G, H, I and other phases (hereinafter Sc). It is reported that a compound and a composition exhibiting a ferroelectric liquid crystal phase are mixed with one or more compounds exhibiting a ferroelectric liquid crystal phase to obtain a whole as a ferroelectric liquid crystal composition. 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. (Mol. Cryst. Liq. Cryst., 89 , 327 (198
2)).

Taken together, it can be seen that a ferroelectric liquid crystal composition can be constituted by using one or more optically active compounds as basic substances regardless of whether or not they exhibit a ferroelectric liquid crystal phase. However, it is preferable that the optically active substance exhibits a liquid crystal phase, if desired. Even 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, a liquid crystal material which has spontaneous polarization required for high-speed response, exhibits low viscosity and exhibits a ferroelectric liquid crystal phase in a wide temperature range including a room temperature range has not been found so far.

Certain of the compounds of the present invention are included in the concept of JP-A-2-131444, but the publication does not disclose any specific physical properties and properties of the compounds.

In addition, complicated protection,
Since a deprotection step is used or a compound having an asymmetric carbon atom is used as a raw material as a method for introducing an asymmetric carbon atom, it is hard to say that it is an industrially advantageous production method because it lacks versatility.

<Problems to be Solved by the Invention> The present invention relates to a ferroelectric liquid crystal material having a sufficient spontaneous polarization, capable of high-speed response, and exhibiting a ferroelectric liquid crystal phase in a temperature region near room temperature, and a component thereof. It is intended to provide a useful phenylpyrimidine derivative and a method for producing the same.

<Means for Solving the Problems> That is, the present invention provides a compound represented by the general formula [1]: (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 or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom,
Is -O-, -COO- or -OCO-, and Ar is a compound of the formula Also Are shown, Y is - (CH _{2 m} or .l showing a -CH = CH- (CH _{2 n,} and s are each 0 or 1, m represents an integer of 0, n is 0 to 8 And the symbol * represents an asymmetric carbon atom.) The present invention relates to a phenylpyrimidine derivative represented by the formula, a synthetic intermediate thereof, a production method thereof, 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.

The compound of the present invention wherein s of the phenylpyrimidine derivative [1] is 1 is represented by the general formula [2] (Wherein, R ¹ , X, Ar, Y, 1, p, and * have the same meanings as described above) and an alcohol represented by the general formula [3] R ² COR ′ [3] (wherein R ² represents the same meaning as described above, R ′ represents a hydroxyl group,
Indicates OCOR ² or a halogen atom. ) Is obtained by reacting with a carboxylic acid represented by

In the reaction between the alcohol [2] and the carboxylic acid [3], the carboxylic acid [3] includes a carboxylic acid having an alkyl group represented by R ² , an acid anhydride or an acid chloride thereof, and an acid bromide. Acid halides such as are used. In addition, these carboxylic acids may be any of a racemic form and an optically active form.

The above reaction is generally performed in the presence or absence of a solvent, generally in the presence of a catalyst.

When a solvent is used in the above reaction, examples of the solvent include ethers 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, such as ketones, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, and aprotic polar solvents, alone or in a mixture. The amount used is not particularly limited.

In the above reaction, when an acid anhydride or an acid halide of an aliphatic carboxylic acid is used, the amount of the acid anhydride to be used is required to be at least 1 equivalent times the alcohol [2], and the upper limit is not particularly limited. Preferably it is 1.1 to 4 equivalent times.

As the catalyst, for example, dimethylaminopyridine, 4
-Pyrrolidinopyridine, triethylamine, tri-n-
Organic or inorganic basic substances such as butylamine, pyridine, picoline, collidine, imidazole, sodium carbonate, sodium methylate, potassium hydrogen carbonate and the like 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 varies depending on the type of the acid anhydride or acid halide of the carboxylic acid and the combination of the catalyst to be used, and is not necessarily specified. For example, when an acid halide is used, it is 1 equivalent to the acid halide. That is all.

In the above reaction, when a carboxylic acid is used,
In the presence of a condensing agent, the carboxylic acid is usually dehydrated and condensed using 1 to 2 equivalents with respect to the alcohol [2] to obtain a phenylpyrimidine derivative (s is 1 in the general formula [1]). Can be.

As the condensing agent, carbodiimides such as N, N'-dicyclohexylcarbodiimide and N-cyclohexyl-N '-(4-diethylamino) cyclohexylcarbodiimide are preferably used.
Organic bases such as dimethylarnopyridine, 4-pyrrolidinopyridine, pyridine and triethylamine are used in combination.

The amount of the condensing agent used is 1 to 1.5 equivalent times with respect to the carboxylic acid, and when the organic base is used in combination, the amount used is
It is 0.01 to 0.2 equivalent times the condensing agent.

The reaction temperature is usually −30 to 100 ° C., preferably 0 to 100 ° C.
~ 80 ° C.

The reaction time is not particularly limited, and the time when the alcohol [2] as the raw material disappears can be regarded as the reaction end point.

After completion of the reaction, normal separation means such as extraction, liquid separation,
A phenylpyrimidine derivative [1]
(Where s = 1) can be obtained in good yield, and if necessary, can be purified by column chromatography, recrystallization or the like.

Next, in the general formula [1], the phenylpyrimidine derivative in which s is 0 is obtained by mixing the alcohol represented by the general formula [2] with the general formula [4] R ² -Z [4] (wherein R ² Has the same meaning as described above, and Z represents a halogen atom or —OSO ₂ R ″, where R ″ represents a lower alkyl group or an optionally substituted phenyl group.) It can be produced by reacting.

Here, the alkylating agent [4], a halide or sulfonic acid ester having a substituent group R ^2, can be prepared by known methods from the corresponding alcohols.

The substituent R ² in the alkylating agent [4] may be an optically active substance.

This reaction is usually performed in the presence of a basic substance.

The amount of the alkylating agent [4] to be used may be 1 equivalent or more relative to the alcohol [2], but is usually 1 to 5 equivalents.
The range of equivalents.

The above reaction is usually performed in the presence of a solvent, and the solvent used is, for example, tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane. , Dimethylformamide, dimethylsulfoxide, hexamethylphosphorylamide, N-methylpyrrolidone and other ethers, ketones, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, aprotic polar solvents and other inert solvents alone. Or a mixture. The amount of the solvent used is not particularly limited.

Examples of the basic substance include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metals such as lithium, sodium, and potassium, alkali metal alcoholates such as sodium ethylate and sodium methylate, sodium carbonate, and potassium carbonate. And butyllithium.

Such a basic substance is 1 to alcohols [2].
The amount is required to be at least equivalent, and the upper limit is not particularly limited, but is usually 1.1 to 5 equivalents.

The reaction temperature is commonly known as -50 to 120 ° C, preferably -30 to 1
It is in the range of 00 ° C.

The reaction time is not particularly limited, and the reaction can be terminated when the raw material alcohol [2] disappears.

After completion of the reaction, the desired phenylpyrimidine derivative represented by the general formula [1] (provided that s is present) from the reaction mixture by a conventional separation means such as extraction, liquid separation, and concentration.
Can be isolated and, if necessary, purified by column chromatography, recrystallization or the like.

Further, in the alkylation reaction, when the substituent Z of the alkylating agent [4] is an iodine atom, silver oxide can be used instead of the above basic substance.

In this case, the silver oxide needs to be at least 1 equivalent times the alcohol [2], and the upper limit is not particularly limited, but is preferably 5 equivalent times.

When the alkylation reaction is carried out in the presence of silver oxide, the amount of the alkylating agent [4] (provided that the substituent Z is an iodine atom) may be 1 equivalent or more times the amount of the alcohols [2]. However, it is preferably 2 to 10 equivalent times.

As a reaction solvent, an excess of an alkylating agent [4] (substituent of which is an iodine atom) can be used as a solvent, and ethers such as tetrahydrofuran, ethyl ether, dioxane, acetone, methyl ethyl ketone, benzene, toluene, and hexane can be used. Solvents which are inert to the reaction, such as ketones or hydrocarbon solvents, may be used alone or as a mixture.

The reaction temperature is usually in the range of 0 to 150 ° C, preferably 20 to 100 ° C.

 The reaction time is usually 1 hour to 20 days.

The removal of the phenylpyrimidine derivative [1] (where s = 0) from the reaction mixture is carried out by removing the silver salt by filtration and then adding a usual post-treatment operation such as extraction, liquid separation, and concentration. Will be

Further, if necessary, it can be purified by column chromatography or the like.

The method for obtaining the phenylpyrimidine derivative from the alcohol [2] has been described above. Examples of the substituent R ² in the carboxylic acid [3] and the alkylating agent [4] used herein include the following.

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, propoxyhexyl , Propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxy Ethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyheptyl, pentyloxyoctyl, pentyloxynonyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl , Hexyloxypentyl, hexyloxyhexyl, hexyloxyheptyl, hexyloxyoctyl Hexyloxy nonyl, hexyloxy decyl, heptyloxy methyl, heptyloxy ethyl, heptyloxy propyl, heptyloxy butyl, heptyloxy pentyl,
Octyloxymethyl, octyloxyethyl, octyloxypropyl, deloxymethyl, 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-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, in the above examples, halo represents fluorine, chlorine, bromine or iodine) and the like.

Further, in the case of carboxylic acids [3], in addition to the above examples, halomethyl, 1-haloethyl, 1-halopropyl,
Examples include 1-halobutyl, 1-halopentyl, 1-halohexyl, 1-haloheptyl, 1-halooctyl, and the like.

These alkyl groups or alkoxyalkyl groups are linear or branched, and when branched, may be an optically active group.

Some optically active among the carboxylic acids having the above-exemplified substituents R ^2, the oxidation of the corresponding alcohol, obtained by reductive deamination of amino acids, or there shall occur naturally, or by resolution It can be derived from the following optically active amino acids and optically active oxyacids obtained.

The optically active Some of alkylating agent having a substituent R ² is, can be easily prepared by known methods from the corresponding alcohol, it is certain of the alcohol, the asymmetric metal catalyst of the corresponding ketone or Obtained by asymmetric reduction with microorganisms or oxygen. Some are naturally occurring or can be derived from the following optically active amino acids or oxyacids obtained by optical resolution.

Alanine, 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, tropic acid, 3-hydroxybutyric acid, malic acid, tartaric acid or isopropylmalic acid and the like.

Further, among the phenylpyrimidine derivatives represented by the general formula [1], compounds wherein Y is-(CH _{2 m} and m is 2 to 10 are represented by the general formula [1 ′] (Wherein, R ¹ , R ² , X, Ar, l, n, s, and * have the same meanings as described above.) Hydrogenation using a hydrogen and a hydrogenation catalyst Can also be manufactured.

As the hydrogenation catalyst used in the above reaction, Raney nickel or a palladium-based metal catalyst is preferably used, and specific examples thereof include palladium-carbon, palladium oxide, palladium black, and palladium chloride.

Such a hydrogenation catalyst is used usually in an amount of 0.001 to 0.5 times, preferably 0.005 to 0.3 times, the weight of the phenylpyrimidine derivative represented by the general formula [1 ']. The reaction is performed in a solvent. Examples of the solvent include water, dioxane, tetrahydrofuran, methanol, ethanol, n-propyl alcohol, acetone, dimethylformamide, toluene, hydrocarbons such as dichloromethane or ethyl acetate,
A single or mixture of solvents inert to the reaction, such as alcohols, ethers, ketones, esters, halogenated hydrocarbons or amides, is used.

The reaction is carried out at a hydrogen pressure of normal pressure or under pressure, and when the amount of absorbed hydrogen becomes 1.0 equivalent times the phenylpyrimidine derivative represented by the general formula [1 '] as the raw material, the reaction end point is determined. Is preferred.

The reaction is carried out at -10 ° C to 100 ° C, preferably at 10 ° C to 60 ° C.

After the reaction is completed, the catalyst is removed from the reaction mixture by filtration or the like, and then concentrated, and the like. In the target general formula (1), Y =-(CH _{2 m} and m = an integer of 2 to 10. A phenylpyrimidine derivative can be obtained, which can be purified, if necessary, by recrystallization or column chromatography, etc. The starting material alcohol represented by the general formula [2] is synthesized as follows. can do.

(In the formula, R ¹ , X, Ar, Y, l, and * represent the same meaning as described above, and R ³ represents a lower alkyl group.) Further, in the general formula (2-b) or (2-c), the synthesis of the compound represented, Y is - (CH _{2 m} or -CH = CH- (CH _2
n (where m is an integer of 2 to 10, and n is an integer of 0 to 8).

(Wherein, R ¹ , X, Ar, l and n have the same meaning as described above, R represents a hydrogen atom or a lower acyl group, and X ′
Represents a bromine or iodine atom. ).

However, R in the general formula (2-C ′) or (2-C ″)
Is a lower acyl group, it can be hydrolyzed and used as an alcohol represented by the general formula (2-C). When Y is-(CH _{2 m} (where m is 0 or 1) Where the above raw materials For example, if Ar in the case of, Can be synthesized.

From the compound represented by the general formula (2-b), the compound represented by the general formula (2-b)
As a method for synthesizing the compound represented by a), the compound represented by the general formula (2-
The compound can be produced by asymmetric hydrolysis using an esterase having the ability to hydrolyze one of the optically active forms of the compound represented by b).

In addition, the esterase in the present invention means esterase in a broad sense including lipase.

The microorganism that produces an esterase used in this reaction may be any microorganism that produces an esterase having the ability to asymmetrically hydrolyze esters, and is not particularly limited.

Specific examples of such microorganisms include, for example, Enterobacter, Arthrobacter, Brevibacterium, Pseudomonas, Alcaligenes, Micrococcus, Chromobacterium, Microbacterium, Corynebacterium, Bacillus, Lactobacillus, Trichoderma, Candida, Saccharomycel, Rhodotorula, Cributococcus, Torulopsis, Pipia, Penicillium, Aspergillus,
Microorganisms belonging to the genera Rhizopus, Mucor, Aureopacidium, Actinomucor, Nocardia, Streptomyces, Hansenula, and Achromobacter are exemplified.

The cultivation of the microorganism is usually performed according to a conventional method, and a culture solution can be obtained by performing liquid culture.

For example, a sterilized liquid medium (malt extract / yeast extract medium for molds and yeasts (heptone 5 g, glucose 10 g, malt extract 3 g, yeast extract 3 g dissolved in water 1, p
H6.5. ), For bacteria, sweetened broth medium (water 1)
10 g of glucose, 5 g of peptone, 5 g of meat extract, and 3 g of NaCl are dissolved in the solution to pH 7.2. )] Inoculated with microorganisms, usually 20
The culture is performed by reciprocating shaking culture at 4040 ° C. for 1 to 3 days, and solid culture may be performed if necessary.

Some of these microbial esterases are commercially available and can be easily obtained. Specific examples of commercially available esterases include, for example, the following.

Pseudomonas lipase [Lipase P (Amano Pharmaceutical)], Aspergillus lipase [Lipase AP (Amano Pharmaceutical)], Mucor lipase (Lipase M-AP)
(Manufactured by Amano Pharmaceutical Co., Ltd.)), lipase of Candida syrindrasse [lipase MY (manufactured by Meito Sangyo)], lipase of the genus Alcaligenes [lipase PL (manufactured by Meito Sangyo)], lipase of the genus Achromobacter [lipase AL (name Sugar industry)),
Lipase of the genus Arthrobacter [lipase joint BSL (joint liquor purification)], lipase of the genus Chromobacterium (manufactured by Toyo Brewery), lipase of Rhizopus delemar [talipase (manufactured by Tanabe Seiyaku)], lipase of the genus Rhizopus [lipase syrup] Ken (Osaka Bacteria Research Institute)].

Also, animal and plant esterases can be used,
Specific examples of these esterases include the following.

Steabsin, pancreatin, pig liver esterase, Wheat Germ esterase.

As the esterase used in this reaction, an enzyme obtained from an animal, a plant, or a microorganism is used. The enzyme may be used in the form of a purified enzyme, a crude enzyme, an enzyme-containing substance, a microorganism culture solution, a culture, a cell, a culture medium, It can be used as needed in various forms such as a liquid and a product obtained by treating them, and a combination of an enzyme and a microorganism can also be used. Alternatively, it can be used as an immobilized enzyme immobilized on a resin or the like, or an immobilized cell.

The asymmetric hydrolysis reaction is generally performed by vigorously stirring a mixture of the compound (2-b) as a raw material and the enzyme or the microorganism in a buffer.

As the buffer, sodium phosphate which is usually used,
A buffer solution of an inorganic acid salt such as potassium phosphate or a buffer solution of an organic acid salt such as sodium acetate or sodium citrate is used, and its pH is 8 to 11 in a culture solution of an alkaliphilic bacterium or an alkaline esterase. For cultures of non-alkaline microorganisms or esterases that are not resistant to alkali
pH 5-8 is preferred. The concentration is usually 0.05-2M, preferably 0.0
It is in the range of 5 to 0.5M.

The reaction temperature is usually from 10 to 60 ° C, and the reaction time is generally from 10 to 70 hours, but is not limited thereto.

When a lipase belonging to the genus Pseudomonas or the genus Arthrobacter is used as the lipase in this asymmetric hydrolysis reaction, an optically active compound (2-a) with relatively high optical purity can be obtained.

In addition, at the time of this asymmetric hydrolysis reaction, an organic solvent which is inert to the reaction, such as toluene, chloroform, methyl isobutyl ketone, or dichloromethane, can be used in addition to the buffer solution. Decomposition can be performed advantageously.

By the asymmetric hydrolysis reaction, the compound (2-
Only one of the optically active forms b) is hydrolyzed to produce the compound (2-a), while the other optically active form of the raw material compound (2-b) is an optically active form. Esters will remain as hydrolysis residues.

After completion of the hydrolysis reaction, the hydrolysis reaction solution is extracted with a solvent such as methyl isobutyl ketone, ethyl acetate, ethyl ether, or the like, and the solvent is distilled off from the organic layer, and the concentrated residue is subjected to column chromatography. The optically active compound (2-a) which is a hydrolysis product and the optically active esters remaining as a hydrolysis residue [the optically active compound in the starting compound (2-b) is not hydrolyzed Can be separated.

The optically active ester obtained here is further hydrolyzed if necessary, and can be converted into an enantiomeric optically active compound (2-a) with the optically active alcohol previously obtained.

From the compound represented by the general formula (2-c), the compound represented by the general formula (2-
As a method for synthesizing the compound represented by b), general formula (2-
The compound represented by c) can be produced by reacting with a carboxylic acid represented by the general formula [8] R ³ COOH [8] (wherein R ³ represents a lower alkyl group) or a derivative thereof. .

In such an acylation reaction, an acid anhydride or an acid halide of a lower alkyl carboxylic acid is usually used as the lower alkyl carboxylic acid {ie, the carboxylic acid [8] or a derivative thereof] as the acylating agent, for example, acetic anhydride. , Propionic anhydride, acetic chloride or bromide, propionic chloride or bromide, butyryl chloride or bromide, valeroyl chloride or bromide, and the like.

The reaction of the compound (2-c) with the lower alkylcarboxylic acid is carried out by applying a usual esterification condition, and using a catalyst in the presence or absence of a solvent.

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

The lower alkyl carboxylic acid [8] used in the above reaction is required to be at least 1 equivalent to the compound (2-c) as a raw material, and the upper limit is not particularly limited, but is preferably.
1.1 to 4 equivalents.

Examples of the catalyst used in the above reaction include organic or inorganic base substances such as dimethylaminopyridine, triethylamine, tri-n-butylamine, pyridine, picoline, imidazole, sodium carbonate, sodium methylate, and potassium hydrogen carbonate. Although the amount of use is not particularly limited, it is generally 1 to 5 with respect to compound (2-c).
5 equivalents.

When an organic amine is used as a solvent, the amine sometimes acts as a catalyst.

Further, acids such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid can be used as the catalyst.

The amount of the catalyst used varies depending on the type of the lower alkyl carboxylic acid and the combination of the catalyst to be used, etc., and cannot always be specified. For example, when an acid halide is used as the lower alkyl carboxylic acid, 1 to the acid halide is used. Used more than equivalent.

The reaction temperature is usually −30 to 100 ° C., preferably −2 to 100 ° C.
0-90 ° C.

The reaction time is not particularly limited, and the starting compound (2-c)
The point at which disappears can be regarded as the end point of the reaction.

After completion of the reaction, usual separation means such as extraction, liquid separation,
The compound (2-b) can be obtained in good yield by operations such as concentration and recrystallization, which can be purified by column chromatography or the like if necessary, but used as a reaction mixture in the next step. You can also.

In the optically active compound (2-a), Y is-(CH ₂
The compound having _m and m of 2 to 10 can be produced by the following method. That is, the general formula (2-a ') (Wherein, R ₁ , Y, Ar, m, n, and * have the same meanings as described above.) A method of hydrogenating an optically active unsaturated alcohol represented by the following formula using hydrogen and a hydrogenation catalyst. is there.

In the above reaction, a Raney nickel palladium-based metal catalyst is preferably used as the hydrogenation catalyst, and specific examples thereof include palladium-carbon, palladium oxide, palladium black, and palladium chloride.

Such a hydrogenation catalyst is used usually in an amount of 0.001 to 0.5 times by weight, preferably 0.005 to 0.3 times by weight, based on the optically active (2-a '). The reaction is carried out in a solvent, such as water, dioxane, tetrahydrofuran, methanol,
Solvents which are inert to the reaction, such as hydrocarbons such as ethanol, n-propyl alcohol, acetone, dimethylformamide, toluene, dichloromethane and ethyl acetate, alcohols, ethers, ketones, esters, halogenated hydrocarbons and amides, alone or in a mixture. used.

The above reaction is carried out at a hydrogen pressure of normal pressure or under pressure, and when the amount of absorbed hydrogen becomes 1 to 1.2 equivalent times the optically active unsaturated alcohol (2-a ') as the raw material. It is preferable to set the reaction end point.

 The reaction is carried out at -10 to 100 ° C, preferably at 10 to 60 ° C.

After completion of the reaction, the target compound can be obtained by removing the catalyst from the reaction mixture by filtration or the like, and then concentrating the same, and can be purified by recrystallization or column chromatography if necessary. it can.

Similarly, in compound (2-b), Y is-(CH ₂
Compounds having _m and m of 2 to 10 can be produced.

Now, the aforementioned Heck reaction (Heck reaction) will be described in more detail.

The compound represented by the general formula (2-C ′) is obtained by combining a halide represented by the general formula 5 with a general formula [6] (Wherein, n and R have the same meanings as described above). The olefins are obtained by reacting with a metal catalyst in the presence of a basic substance.

The starting compounds represented by the general formulas [5] and [6]
It can be produced according to the method described in the literature.

The amount of the olefin [6] used is the halide [5]
Is usually 0.9 to 10 equivalents, preferably 1 to
It is twice equivalent.

As the metal catalyst used in the above reaction, palladium chloride, palladium acetate, triphenylphosphine palladium complex, palladium / carbon and the like are used in the case of palladium, and the same catalysts as described above are used in the case of nickel and rhodium.

The amount of these metal catalysts used is in the range of 10 ^-3 to 10 ^-1 times equivalent to the starting halide [5].

In this reaction, in addition to the metal catalyst, 3
A trivalent phosphorus compound or a trivalent arsenic compound is required,
These include the general formula [7] (In the formula, M represents a phosphorus atom or an arsenic atom, and R ⁴ , R ^5, and R ⁶ are the same or different and represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom.) Specific examples of the compound include tri-n-butylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-o-tolylphosphite, phosphorus trichloride, and triphenylarsenic.

These phosphorus compounds or arsenic compounds are used in an amount of 0.5 to 50 equivalents, preferably 10
~ 30 equivalents.

Examples of the basic substance include alkali metal carbonates, carboxylate salts, alkoxides, hydroxides, and organic bases, and tertiary amines or alkali metal carbonates are preferably used. Examples thereof include di-isopropylethylamine, tri-n-butylamine, tetramethylethylenediamine, dimethylaniline, sodium carbonate, and sodium hydrogencarbonate.

The amount of the basic substance used is 1 to 5 equivalents to the halide [5].

If necessary, for example, acetonitrile, tetrahydrofuran, dimethylformamide, hexamethylphosphorylamide, N-methylpyrrolidone, methanol or the like can be used as a reaction solvent.

 The use amount of these reaction solvents is not particularly limited.

This reaction is usually performed in an inert gas such as nitrogen or argon.

In this method, the yield of the target compound (2-b) can be improved by increasing the reaction temperature. However, if the temperature is too high, by-products increase. Yes, preferably 100-150 ° C.

After completion of the reaction, the compound (2-b) can be obtained by ordinary means such as extraction, distillation, recrystallization and the like.

Examples of the phenylpyrimidine derivative represented by the general formula (1) obtained by the method described above include the following.

5- {alkyl (C3-20)}-2- (4-substituted phenyl) pyrimidine, 2- {alkyl (C3-20)}-5- (4-substituted phenyl) pyrimidine, 5- {Alkyl (C3-20) oxy} -2-
(4-substituted phenyl) pyrimidine, 2- {alkyl (C3-20) oxy} -5-
(4-substituted phenyl) pyrimidine, 2- {alkyl (C3-20) oxyphenyl}
-5-substituted pyrimidine, 5- {alkyl (C3-20) carbonyloxy} -2- (4-substituted phenyl) pyrimidine, 2- {alkyl (C3-20) carbonyloxy} -5- (4-substituted phenyl) pyrimidine, 2- {alkyl (3 to 20 carbon atoms) carbonyloxyphenyl} -5-substituted pyrimidine, 5- {alkyl (3 to 20 carbon atoms) oxycarbonyl-2- (4- (Substituted phenyl) pyrimidine, 2- {alkyl (3-20 carbon atoms) oxycarbonylphenyl} -5-substituted pyrimidine, wherein “substituted” in the compound names indicates the following substituents.

1-alkyl (R ²⁾ oxy-2,2,2-trifluoroethyl 2-alkyl (R ²⁾ oxy-3,3,3-trifluoro -
1-propyl, 3-alkyl (R ²⁾ oxy -4,4,4-trifluoro -
1-butyl, 4-alkyl (R ²⁾ oxy trifluoro -
1-pentyl, 5-alkyl (R ² ) oxy-6,6,6-trifluoro-
1-hexyl, 6-alkyl (R ² ) oxy-7,7,7-trifluoro-
1-heptyl, 7- alkyl (R ²⁾ oxy -8,8,8- trifluoro -
1-octyl, 8-alkyl (R ² ) oxy-9,9,9-trifluoro-
1-nonyl, 9-alkyl (R ²⁾ oxy -10,10,10- trifluoro-1-decyl, 10- alkyl (R ²⁾ oxy -11,11,11- trifluoro-1-undecyl, 11- Alkyl (R ² ) oxy-12,12,12-trifluoro-1-dodecyl, 3-alkyl (R ² ) oxy-4,4,4-trifluoro-
1-butenyl, 4-alkyl (R ²⁾ oxy trifluoro -
1-pentenyl, 5-alkyl (R ² ) oxy-6,6,6-trifluoro-
1-hexenyl, 6-alkyl (R ² ) oxy-7,7,7-trifluoro-
1-heptenyl, 7-alkyl (R ²⁾ oxy -8,8,8- trifluoro -
1-octenyl, 8-alkyl (R ²⁾ oxy -9,9,9- trifluoro -
1-nonenyl, 9-alkyl (R ²⁾ oxy -10,10,10- trifluoro-1-decenyl, 10-alkyl (R ²⁾ oxy -11,11,11- trifluoro-1-undecenyl, 11- Alkyl (R ² ) oxy-12,12,12-trifluoro-1-dodecenyl, wherein alkyl (R ² ) is an alkoxyalkyl having 2 to 20 carbon atoms which may be substituted by a halogen atom exemplified above. Represents a group. Furthermore, 1-alkyl (R ²⁾ carbonyloxy-2,2,2 trifluoride ethyl 2-alkyl (R ²⁾ carbonyloxy-3,3,3-trifluoro-1-propyl, 3-alkyl (R ²⁾ Carbonyloxy-4,4,4-trifluoro-1-butyl, 4-alkyl (R ² ) carbonyloxy-5,5,5-trifluoro-1-pentyl, 5-alkyl (R ² ) carbonyloxy-6 , 6,6-Trifluoro-1-hexyl, 6-alkyl (R ² ) carbonyloxy-7,7,7-trifluoro-1-heptyl, 7-alkyl (R ² ) carbonyloxy-8,8,8 - trifluoro-1-octyl, 8-alkyl (R ²⁾ carbonyloxy -9,9,9- trifluoro-1-nonyl, 9-alkyl (R ²⁾ carbonyloxy -10,10,10- trifluoro - 1-decyl, 10- alkyl (R ²⁾ carbonyloxy -11 11,11-trifluoro-1-undecyl, 11-alkyl (R ² ) carbonyloxy-12,12,12-trifluoro-1-dodecyl, 3-alkyl (R ² ) carbonyloxy-4,4,4- trifluoro-1-butenyl, 4-alkyl (R ²⁾ carbonyloxy -5,5,5-trifluoro-1-pentenyl, 5-alkyl (R ²⁾ carbonyloxy -6,6,6- trifluoro -1 - hexenyl, 6- alkyl (R ²⁾ carbonyloxy -7,7,7- trifluoro-1-heptenyl, 7-alkyl (R ²⁾ carbonyloxy -8,8,8- trifluoro-1-octenyl, 8 - alkyl (R ²⁾ carbonyloxy -9,9,9- trifluoro-1-nonenyl, 9-alkyl (R ²⁾ carbonyloxy -10,10,10--trifluoro-1-decenyl, 10-alkyl (R ²⁾ carbonyloxy -11,11,11- trifluoride 1-undecenyl, 11- alkyl (R ²⁾ carbonyloxy -12,12,12--trifluoro-1-dodecenyl, where the alkyl (R ²⁾ may be substituted with a halogen atom exemplified in the above Represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms.

Examples of the optically active alcohol represented by the general formula (2-a) include 5-alkyl-2- (1-hydroxy-2,2,2-trifluoro-ethyl) phenylpyrimidine, 5-alkyloxy-2- (1-hydroxy-2,2,2
-Trifluoro-ethyl) phenylpyrimidine, 5-alkylcarbonyloxy-2- (1-hydroxy-2,2,2-trifluoro-ethyl) phenylpyrimidine, 5-alkyloxycarbonyl-2- (1-hydroxy-2 , 2,2-trifluoro-ethyl) phenylpyrimidine, 2-alkylphenyl-5- (1-hydroxy-2,2,
2-trifluoro-ethyl) pyrimidine, 2-alkyloxyphenyl-5- (1-hydroxy-2,2,2-trifluoro-ethyl) pyrimidine, 2-alkylcarbonyloxyphenyl-5- (1-
(Hydroxy-2,2,2-trifluoro-ethyl) pyrimidine, 2-alkyloxycarbonyloxyphenyl-5-
(1-hydroxy-2,2,2-trifluoro-ethyl) pyrimidine, 2-alkyl-5- (1-hydroxy-2,2,2-trifluoro-ethyl) phenylpyrimidine, 2-alkyloxy-5- (1-hydroxy-2,2,2
-Trifluoro-ethyl) phenylpyrimidine, 2-alkylcarbonyloxy-5- (1-hydroxy-2,2,2-trifluoro-ethyl) phenylpyrimidine, 2-alkyloxycarbonyl-5- (1-hydroxy-2 , 2,2-trifluoro-ethyl) phenylpyrimidine and the substituent (1-hydroxy-2,2,2-trifluoro-ethyl) group are 2-hydroxy-3,3,3-trifluoro-propyl, 3- Hydroxy-4,4,4-trifluoro-butyl, 4-hydroxy-5,5,5-trifluoro-pentyl, 5-hydroxy-6,6,6-trifluoro-hexyl, 6-hydroxy-7,7 , 7-Trifluoro-heptyl, 3-hydroxy-4,4,4-trifluoro-1-butenyl, 4-hydroxy-5,5,5-trifluoro-1-pentenyl, 5-hydroxy-6,6, 6-trifluoro -1-hexenyl, 6-hydroxy-7,7,7-trifluoro-1-heptenyl, 7-hydroxy-8,8,8-trifluoro-octyl, 8-hydroxy-9,9,9-trifluoro- Nonyl, 9-hydroxy-10,10,10-trifluoro-decyl, 10-hydroxy-11,11,11-trifluoro-undecyl, 11-hydroxy-12,12,12-trifluoro-dodecyl, 7-hydroxy -8,8,8-trifluoro-1-octenyl, 8-hydroxy-9,9,9-trifluoro-1-nonenyl, 9-hydroxy-10,10,10-trifluoro-1-decenyl, 10- Compounds substituted with either hydroxy-11,11,11-trifluoro-1-undecenyl or 11-hydroxy-12,12,12-trifluoro-1-dodecenel are exemplified.

Here, alkyl in a compound name shows a C1-C20 alkyl group.

The liquid crystal composition of the present invention contains at least one phenylpyrimidine derivative represented by the above general formula [1] as a compounding component. In this case, the general formula [1]
The compound represented by, 0.1 ~ 99.9 of the resulting liquid crystal composition
%, 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 can be a conventionally known method, and is not particularly limited. Not something.

The phenylpyrimidine derivative represented by the general formula [1] of the present invention can be used without increasing the viscosity by forming a liquid crystal composition even when it does not show a liquid crystal phase by itself.

As the phenylpyrimidine derivative represented by the general formula [1], a compound in which Y is CH _{2 m} is particularly preferable from the viewpoint of chemical stability. From the viewpoint of liquid crystal properties, m is 2
The above is preferred.

Further, when s = 1, the liquid crystal composition is excellent in enhancing the spontaneous polarization, and can also increase the response speed.

<Effect of the Invention> The phenylpyrimidine derivative represented by [1] in the general formula of the present invention has very excellent properties as a liquid crystal compound, and thus is effectively used as a liquid crystal composition and further as a liquid crystal device using the same. can do.

<Examples> Hereinafter, the present invention will be described in more detail by way of examples,
The present invention is not limited to these examples.

Reference Example 1 In a four-necked flask equipped with a stirrer and a thermometer, 2-
(4-bromophenyl) -5-decyloxypyrimidine
78 g (0.2 mol), 1,1,1, -trifluoro-acetoxin-3-butene 46 g (0.3 mol), sodium hydrogen carbonate 50 g
And N-methylpyrrolidone 150 ml, in a nitrogen atmosphere 1.6 g of triphenylphosphine and 0.6 g of palladium acetate
Was added and the mixture was heated and stirred at 110 to 120 ° C. for 20 hours.

After completion of the reaction, the reaction mixture was poured into 500 ml of water and extracted with 500 ml of toluene. The obtained toluene layer was washed with water and then concentrated under reduced pressure to obtain a blackish residue.

This was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give 2- {4-
(3-acetoxy 4,4,4-trifluoro-1-butenyl) phenyl} -5-decyloxypyrimidine (10-1)
42 g (yield 45%) were obtained.

23 g (5 mmol) of (10-1) obtained here were mixed with 500 ml of 0.3 M phosphate buffer (pH 7.0), 10 ml of chloroform and 3 g of Pseudomonas lipase (lipase "p" amano).
And stirred vigorously at 36-38 ° C. for 30 hours.

The obtained mixture was extracted with 200 ml of toluene, and the organic layer was washed with water and then concentrated under reduced pressure.

The obtained residue was separated by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (-)-2.
-{4- (3-hydroxy-4,4,4-trifluoro-1
-Butenyl) phenyl} -5-decyloxypyrimidine (2-a-1) 10 g (yield 48%), ▲ [a] ²⁰ _D ▼ = -1
5.1 ゜ (c = 1, chloroform) and (−)-2-
｛4- (3-acetoxy-4,4,4-trifluoro-1-
(Butenyl) phenyl} -5-decyloxypyrimidine 1
1.8 g (50% yield), ▲ [a] ²⁰ _D ▼ = -4.5 ゜ (c = 1,
Chloroform). 4.2 g of (2-a-1) obtained here
(1 mmol) in 20 ml of tetrahydrofuran and 10
After adding 0.05 g of% pd / c, a hydrogenation reaction was performed under a hydrogen atmosphere under normal pressure. When about 230 ml of hydrogen was consumed, the reaction was stopped, 10% pd / C was filtered off, and the filtrate was concentrated.
4.2 g of (-)-2- {4- (3-hydroxy-4,4,4-trifluoro-butyl) phenyl} -5-decyloxypyrimidine (100% yield), ▲ [a] ²⁰ _D ▼ = -14.9 ゜ (c
= 1, chloroform).

Reference Examples 2 to 5 Except that 2- (4-bromophenyl) -5-decyloxypyrimidine and 1,1,1 trifluoro-2-acetoxy-3-butene of Reference Example 1 were replaced with the compounds shown in Table 1. The reaction and post-treatment were carried out according to Reference Example 1, and
Were obtained.

Example 1 1.0 g of (-)-2- {4- (3-hydroxy-4,4,4-trifluoro-1-butenyl) phenyl} -5-decyloxypyrimidine was dissolved in 5 ml of butyl iodide, and silver oxide was added. Three
g was added and the mixture was stirred at 25-30 ° C for 4 days. After the reaction,
After filtration to remove silver oxide, the residue was concentrated under reduced pressure, and the resulting residue was purified by silica gel color chromatography (eluent: toluene-ethyl acetate) to give (-)-2
-{4- (3-butoxy-4,4,4-trifluoro-1-
(Butenyl) phenyl} -5-decyloxypyrimidine 0.
98 g were obtained.

(-)-2- {4- (3-butoxy-4,4,
0.5 g of 4-trifluoro-1-butenyl) phenyl-5-decyloxypyrimidine was dissolved in 20 ml of tetrahydrofuran, 0.05 g of 10% pd / c was added, and a hydrogenation reaction was performed in a hydrogen atmosphere under normal pressure. The reaction was stopped when about 25 ml of hydrogen was consumed, 10% pd / c was filtered off, the filtrate was concentrated, and the obtained residue was subjected to silica gel column chromatography (eluent: toluene-ethyl acetate). Purified,
0.45 g of (-)-2- {4- (3-butoxy-4,4,4-trifluoro-1-butyl) phenyl} -5-decyloxypyrimidine was obtained.

Example 2 (-)-2- {4- (3-Hydroxy-4,4,4-trifluoro-1-butenyl) phenyl} -5-decyloxypyrimidine (1.0 g) was dissolved in pyridine (20 ml), and butyryl chloride (0.5) was dissolved. g was added and stirred at 25-30 ° C for 4 hours. After completion of the reaction, the reaction mixture was diluted with 100 ml of toluene, washed with 4N hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and water in that order, and then the toluene layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: toluene-ethyl acetate).
1.08 g of (+)-2- (4- (3-butyryloxy-4,4,4-trifluoro-1-butenyl) phenyl} -5-decyloxypyrimidine was obtained.

(+)-2- {4- (3-butyryloxy-4,4,4-trifluoro-1-butenyl) phenyl-5- obtained above
0.5 g of decyloxypyrimidine in 20 ml of tetrahydrofuran
, And 0.05 g of 10% pd / c was added, and a hydrogenation reaction was performed in a hydrogen atmosphere under normal pressure. When about 25 ml of hydrogen was consumed, the reaction was stopped, 10% pd / c was separated by filtration, the filtrate was concentrated, and the obtained residue was subjected to silica gel column chromatography (eluent: toluene-ethyl acetate). Purified,
1.4 g of (+)-2- {4- (3-butyryloxy-4,4,4-trifluoro-1-butyl) phenyl} -5-decyloxypyrimidine was obtained.

Example 3 1.1 g (2.5 mmol) of (-)-2- {4- (4-hydroxy-5,5,5-trichloro-1-pentyl) phenyl} -5-decyloxypyrimidine was dissolved in 10 ml of tetrahydrofuran, and hydrogen was dissolved therein. 0.12 g of potassium iodide (3 mmol)
Was added, and the mixture was stirred at 10 to 20 ° C for 20 minutes. Then, 0.85 g (3 mmol) of octyl p-toluenesulfonate was added, and the mixture was reacted at 20 to 30 ° C for 2 hours. After completion of the reaction, 100 ml of water and 100 ml of toluene
After pouring into toluene, the toluene layer was washed with water and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give (-)-2- {4- (4-octyloxin 5,5,5).
0.80 g of (trifluoro-1-pentyl) phenyl} -5-decyloxypyrimidine was obtained.

Example 4 1.1 g (2.5 mmol) of (-)-2- {4- (4-hydroxy-5,5,5-trichloro-1-pentyl) phenyl} -5-decyloxypyrimidine was dissolved in 10 ml of pyrimidine, 0.53 g (3 mmol) of ilchloride was added and reacted at 20-30 ° C for 2 hours.

After completion of the reaction, the mixture was diluted with 100 ml of toluene, and the toluene layer was
The mixture was washed with N hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and water in that order, and concentrated under reduced pressure.

The obtained residue was purified by silica gel column chromatography (eluent: toluene-ethyl acetate),
(+)-2- {4- (4-nonanoyloxy-5,5,5-
1.25 g of trifluoro-1-pentyl) phenyl} -5-decyloxypyrimidine were obtained.

The results of the compounds obtained in Examples 1 to 4 are shown in Table 1.
2

Examples 5 to 34 The reaction and post-treatment were carried out in the same manner as in any of Examples 1 to 4, except that the raw materials shown in Table 2 were used, and the results shown in Table 2 were obtained.

Example 30 A liquid crystal composition shown in Table 3 was prepared using a liquid crystal compound. 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. A glass fiber (diameter: 5 μm) so that the rubbing directions of the two substrates are parallel. Was used as a spacer to assemble a liquid crystal cell, and the liquid crystal composition (compound) was vacuum-sealed into the liquid crystal cell 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 switching element was used.

Example 31 The spontaneous polarization value and response speed of the compound of the present invention were measured. The results are shown in Table-4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B53 / 00 C07B53 / 00E C07M 7:00 (72) Inventor Masayoshi Minami 2-10-1 Tsukahara, Takatsuki-shi, Osaka No. Within Sumitomo Chemical Co., Ltd. (72) Inventor Takeshi Tani6, Kitahara, Tsukuba, Ibaraki Pref. Within Sumitomo Chemical Co., Ltd. Inventor Koichi Fujisawa 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. (56) References JP-A-2-174166 (JP, A) JP-A-1-301667 (JP, A) JP-A-1-207280 (JP, A) JP-A-61-215372 (JP, A) JP-A-2-229174 (JP, A) JP-A-2-127 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C07D 239/20 C07D 239/34 C09K 19/34 CA (STN) REGISTRY (STN)

Claims (12)

(57) [Claims] 1. The general formula [1] (Wherein, R ¹ represents an alkyl group having 3 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom. , X represents -O-, -COO- or -OCO-, and Ar represents a formula Or Are shown, Y is - (CH _{2 m} or .l and s indicates a -CH = CHCH _{2 n} each represent 0 or 1, m is 0
10 represents an integer, n represents an integer of 0 to 8, and * represents an asymmetric carbon atom. A phenylpyrimidine derivative represented by the formula: 2. The method according to claim 1, wherein Y is CH _{2 m} and s
Is a phenylpyrimidine derivative. 3. The method according to claim 1, wherein Y is CH _{2 m} and s
Is a phenylpyrimidine derivative. 4. The method according to claim 2, wherein Ar is A phenylpyrimidine derivative which is 5. The method according to claim 3, wherein Ar is A phenylpyrimidine derivative which is 6. The method according to claim 1, wherein Y is -CH = CH- (CH ₂
a phenylpyrimidine derivative represented by _n . 7. The general formula (Wherein, R ¹ represents an alkyl group of 3 to 20, X is —O—,
-COO- or -OCO-, wherein Ar is a group represented by the formula Are shown, Y is - (CH _{2 m} or .l showing a -CH = CH- (CH _{2 n} represents 0 or 1, m represents an integer of 0, n is an integer of 0 to 8 , * Indicates an asymmetric carbon atom.) 8. The general formula [2] (Wherein, R ¹ represents an alkyl group of 3 to 20, X is —O—,
-COO- or -OCO-, wherein Ar is a group represented by the formula Are shown, Y is -. (CH _{2 m} or -CH = CH- shows the (CH _{2 n} l represents 0 or 1, m represents an integer of 0, n is an integer of 0 to 8 , * Represents an asymmetric carbon atom) and an alcohol represented by the general formula: R ² COR ′ (wherein, R ² is an alkyl group or carbon atom having 1 to 20 carbon atoms which may be substituted with a halogen atom) 2-20 shows an alkoxyalkyl an alkyl group, R 'is an hydroxyl group, a phenylpyrimidine derivative represented by the general formula which comprises reacting a carboxylic acid represented by.) showing a OCOR ² or halogen atom [1] A method for producing a compound wherein s is 1. 9. An alcohol represented by the general formula [2] and a compound represented by the general formula R ² -Z, wherein R ² is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, And Z represents a halogen atom or —OSO ₂ R ″.
Is shown. Here, R ″ represents a lower alkyl group or a phenyl group which may be substituted.) Among the phenylpyrimidine derivatives represented by the general formula [1], A process for producing a compound wherein is 0. 10. The general formula (Wherein, R ¹ represents an alkyl group having 3 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom. , X represents -O-, -COO- or -OCO-, and Ar represents a formula Or And l and s each represent 0 or 1, n represents an integer of 0 to 8, and * represents an asymmetric carbon atom. A) a general formula wherein the phenylpyrimidine derivative represented by the formula (1) is hydrogenated using hydrogen and a hydrogenation catalyst. (Wherein, R ¹ , R ² , X, Ar, l, s, n, and * represent the same meanings as described above). 11. A liquid crystal composition comprising the phenylpyrimidine derivative according to claim 1 as at least one compounding component. 12. A liquid crystal device comprising a liquid crystal composition containing at least one phenylpyrimidine derivative according to claim 1 as a compounding component.