JP3170913B2 - Optically active pyrimidine compound, production method thereof and liquid crystal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optically active pyrimidine compound, and more particularly to an optically active pyrimidine compound useful as a liquid crystal compound, a method for producing the same, and a liquid crystal composition containing the same.

[0002]

2. Description of the Related 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. A new TN-type display element having a twist angle of 180 to 270 ° has been developed, but the response speed is still insufficient. Although various improvements have been made in this way,
A TN type display element having a high response speed has not been realized.
However, a new display system using a ferroelectric liquid crystal, which has been actively studied recently, has a possibility of remarkably improving the response speed (Clark et al .; Applied. Ph.
ys. Lett., 36, 899 (1980)). This method uses ferroelectric chiral smectic C phase (hereinafter abbreviated as Sc *).
And the like using a chiral smectic phase. 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. Further, not only a ferroelectric liquid crystal composition comprising only a ferroelectric liquid crystal compound, but also
No. 187 discloses non-chiral smectic C, F,
A compound or a composition exhibiting a phase such as G, H, I or the like (hereinafter abbreviated as a phase such as Sc or the like) is used as a basic substance, and one or more compounds exhibiting a ferroelectric liquid crystal phase are mixed with the compound and the whole. To be obtained as a ferroelectric liquid crystal composition. Further, a compound or composition exhibiting a phase such as Sc is used as a basic substance, and one or more compounds which 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. Cry
st. Liq. Cryst., 89, 327 (1982)). 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. Preferably, the optically active substance preferably exhibits a liquid crystal phase,
Even when it 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. Recently, a liquid crystal compound having a fluorine atom has been found (JP-A-3-31243). 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.

[0003]

In recent years, the use of liquid crystals has increased, and the development of liquid crystals having a new structure has been demanded. An object of the present invention is to develop a novel liquid crystal optically active compound having a highly polar fluoroalkyl group on an asymmetric carbon adjacent to a phenyl group.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have reached the present 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 an optically active pyrimidine compound useful as a component thereof and the same. Provide a manufacturing method. That is, the present invention provides a compound represented by the general formula 1 (Wherein, R represents a fluoroalkyl group having 1 or 2 carbon atoms, R ¹ represents an alkyl group having 1-15 carbon atoms, and R ² represents an alkyl group having 1-15 carbon atoms which may be substituted with a halogen atom. A group or an alkoxyalkyl group having 2 to 15 carbon atoms, Y represents -O-, -COO- or -OCO-, and A represents Wherein X represents a hydrogen atom or a halogen atom. m and s each represent 0 or 1. * Indicates an asymmetric carbon atom. The present invention relates to an optically active pyrimidine compound represented by the formula (1), a method for producing the compound, a liquid crystal composition containing at least one of the compounds, and a liquid crystal device using the same.

Hereinafter, the present invention will be described in detail. The optically active pyrimidine compound (Formula 1) of the present invention can be produced by the following method. That is,
General formula 2 (Wherein, R ¹ , A, X, Y and m have the same meanings as described above) and a phenol derivative represented by the following general formula: (Wherein, Z represents a halogen atom or a hydroxyl group; R, R
² , s and * have the same meaning as described above. )) To react with an optically active carboxylic acid.

Here, specific examples of the substituent R ¹ in the general formula (Formula 2) include methyl, ethyl, propyl, butyl,
Examples include pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

Specific examples of the substituent R ² in the general formula (Formula 3) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, 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, pentyloxy Pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxy Pentyl, pentyloxyhexyl, pentyloxyheptyl, pentyloxyoctyl, pentyloxynonyl, pentyloxydecyl, pentyloxymethyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyheptyl, Pentyloxyoctyl, pentyloxynonyl, pentyloxydecyl, hexyloxymethyl,
Hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, hexyloxyheptyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxy Butyl,
Heptyloxypentyl, octyloxymethyl, octyloxyethyl, octyloxypropyl, octyloxybutyl, octyloxypentyl, nonyloxymethyl, nonyloxyethyl, nonyloxypropyl,
Nonyloxybutyl, nonyloxypentyl, decyloxymethyl, decyloxyethyl, decyloxypropyl, decyloxybutyl, decyloxypentyl, 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 2 -Methylpropyl, 2-methylbutyl, 2,3-dimethylbutyl, 2,
2,3-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-Halo3,3 Dihalobutyl, 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-monomethylpentyl-4-methylpentyl, 2-halohexyl, 3-halohexyl, 4-halohexyl, 5-halohexyl, 6-halohexyl, 2-haloheptyl, 2-halooctyl, 2-{(2-haloethoxy) ethyl, 2-}
(3─halopropoxy) ethyl, 2─ (4─halobutoxy) ethyl, 2─ (5─halopentyloxy) ethyl,
2- (5-halohexyloxy) ethyl, 3- (2-haloethoxy) propyl, 3- (3-halopropoxy) propyl, 3- (4-halobutoxy) propyl, 3- (5
{Halopentyloxy) propyl, 4 {(2) haloethoxy) butyl, 4} (3) halopropoxy) butyl,
{(4-halobutoxy) butyl, 5- (2-haloethoxy) pentyl, 5} (3-halopropoxy) pentyl,
6─ (4─haloethoxy) hexyl (however, halo in the above alkyl group means fluorine, chlorine, bromine or iodine)
And the like. Carbon number 1 represented as a substituent R
Alternatively, examples of the 2 fluoroalkyl groups include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl.

A phenol derivative (Chemical Formula 2) which is a raw material of an optically active pyrimidine compound (Chemical Formula 1) is a known compound, and an optically active carboxylic acid (Chemical Formula 3) can be synthesized by the following method.

[0009]

For the reaction between the optically active carboxylic acid (Chemical Formula 3) and the phenol derivative (Chemical Formula 2), a usual esterification method can be applied, and a catalyst or a condensing agent is used in the presence or absence of a solvent. The reaction can be performed by using If a solvent is used in this reaction,
As the solvent, for example, tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene,
Solvents that are inert to the reaction of aliphatic or aromatic hydrocarbons such as benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane or pyridine, ethers, halogenated hydrocarbons, and organic amines Or a mixture. The amount of such a solvent can be used without any particular limitation.

In this reaction, since the optically active carboxylic acids (Chemical Formula 3) are relatively expensive, the phenol derivative (Chemical Formula 2), which is the other raw material, is used in an excessive amount in order to use the carboxylic acids effectively. The reaction is preferably carried out, usually using 1 to 4 equivalents, preferably 1 to 2 equivalents. When a catalyst is used, examples of such a catalyst include organic or inorganic basic substances such as dimethylaminopyridine, tri-n-butylamine, pyridine, lysine, imidazole, sodium carbonate, sodium methylate, and potassium hydrogen carbonate. Further, an organic acid or an inorganic acid such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid can be used as a catalyst.

The amount of the catalyst used depends on the type of each raw material to be used and the combination of the catalyst to be used, etc., and cannot always be specified. For example, when an acid halide is used, it is at least 1 equivalent to the acid halide. Are used. When the optically active carboxylic acid (formula 3) is a carboxylic acid, carbodiimides such as N, N-dicyclohexylcarbodiimide and N-cyclohexyl-N ′-(4-diethylamino) cyclohexylcarbodiimide are preferable as the condensing agent. It is used, and if necessary, an organic base such as 4-pyrrolidinopyridine, pyridine or triethylamine can be used in combination. In this case, the amount of the condensing agent used is usually 1 to 1.2 equivalent times based on the optically active carboxylic acid (3). When an organic base is used in combination, the amount of the organic base used is based on the condensing agent. 0.01 ~
It is 0.2 equivalent times.

The reaction temperature of the reaction between an optically active carboxylic acid (Chemical Formula 3) and a phenol derivative (Chemical Formula 2) is usually
30 ° C to 100 ° C, preferably -25 ° C to 80 ° C
It is. The reaction time is not particularly limited, and the reaction can be terminated by disappearance of the optically active carboxylic acid (Chemical Formula 3) as a raw material. After completion of the reaction, the desired optically active pyrimidine compound represented by the general formula (Chemical Formula 1) can be isolated from the reaction mixture by a conventional separation means, for example, an operation such as extraction, liquid separation, and concentration. It can be purified by column chromatography, recrystallization and the like.

According to the production method described above, an optically active pyrimidine compound (Chemical Formula 1) can be obtained. When this compound is used as a component of a liquid crystal, particularly, a component of a ferroelectric liquid crystal, the compound represented by the general formula (1) It is preferred that the substituent R ² in 1) is an alkyl group or an alkoxyalkyl group containing no halogen atom.

The liquid crystal composition of the present invention contains at least one optically active pyrimidine compound represented by the general formula (1) as a compounding component. The liquid crystal composition contains 0.1 to 99.9% by weight, particularly preferably 1 to 99% by weight of the liquid crystal composition from which the optically active pyrimidine compound (Chem. 1) can be obtained. In addition, by using such a liquid crystal composition, a liquid crystal element, for example, can be effectively used as an optical switching element. In this case, a method of using the liquid crystal composition can be a known method, and is not particularly limited. .

[0016]

The optically active pyrimidine compound represented by the general formula (Chemical Formula 1) has very excellent properties as a liquid crystal compound. Among them, the compound having the Sc * phase is one component of the liquid crystal composition. Is effective in widening the temperature range of the Sc * phase. Further, even a compound that does not exhibit a Sc * phase by itself can be effectively used as a component that induces spontaneous polarization of a liquid crystal composition. Due to the above excellent properties, the optically active pyrimidine compound (Formula 1) of the present invention can be effectively used as a liquid crystal composition and further as a liquid crystal device using the same.
Further, according to the method of the present invention, an optically active pyrimidine compound (Chemical Formula 1) can be easily obtained at a high yield, which is industrially advantageous.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Optically active (+)-4- (1-hexyloxy-2,
Dissolve 3.04 g (10 mmol) of 2,2-trifluoroethyl) benzoic acid, 3.28 g (10 mmol) of 5-decyloxy-2- (p-hydroxyphenyl) pyrimidine and 0.2 g of 4-pyrrolidinopyridine in 20 ml of dry dichloromethane, 2.5 g (12 mmol) of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for 6 hours. After the reaction,
After adding 5% acetic acid aqueous solution and extracting with dichloromethane, the organic layer is sequentially washed with water and a 7% aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is purified by silica gel column chromatography. And optically active (+)-4- (1-hexyloxy-2,2,
5.0 g of 2-trifluoroethyl) benzoic acid 5-decyloxy-2- (p-hydroxyphenyl) pyrimidine
(82% yield). Spontaneous polarization: -240 nC / cm ² (20 ° C)

Example 2 Optically active (+)-4- (1-hexyloxy-2,
3.04 g (10 mmol) of 2,2-trifluoroethyl) benzoic acid, 3.00 g (10 mmol) of 5-octyloxy-2- (p-hydroxyphenyl) pyrimidine and 0.2 g of 4-pyrrolidinopyridine were dried in 20 ml of dichloromethane.
And dissolved in 2.5 g of dicyclohexylcarbodiimide (12 g
Mmol) and stirred at room temperature for 6 hours. After completion of the reaction, 5% aqueous acetic acid was added, and the mixture was extracted with dichloromethane.
The organic layer was washed successively with water and a 7% aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, evaporated, and purified by silica gel column chromatography to obtain optically active (+)-4- (1-). Hexyloxy-2,
2,2-trifluoroethyl) benzoic acid 5-octyloxy-2- (p-hydroxyphenyl) pyrimidine
4.75 g (81% yield) was obtained. Spontaneous polarization: -220 nC / cm ² (25 ° C)

Example 3 Optically active (+)-4- (1-hexyloxy-2,
3.04 g (10 mmol) of 2,2-trifluoroethyl) benzoic acid, 5-decyl-2- (p-hydroxyphenyl)
3.12 g (10 mmol) of pyrimidine and 0.2 g of 4-pyrrolidinopyridine were dissolved in 20 ml of dry dichloromethane, and 2.5 g (12 mmol) of dicyclohexylcarbodiimide was added, followed by stirring at room temperature for 6 hours. 5% after completion of reaction
After adding acetic acid aqueous solution and extracting with dichloromethane, the organic layer is washed with water and a 7% aqueous sodium hydrogen carbonate solution sequentially,
After drying over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is purified by silica gel column chromatography, and optically active (+)-4- (1-hexyloxy-2,2,2-trifluoroethyl) benzoic acid 5-decyl- 2- (p
-Hydroxyphenyl) pyrimidine 4.97 g (83% yield)
I got [Α] _D ²⁵ = −25.0 (CHCl ₃ , C = 1.5)

Example 4 Optically active (+)-4- (1-hexyloxy-2,
Dissolve 3.04 g (10 mmol) of 2,2-trifluoroethyl) benzoic acid, 3.28 g (10 mmol) of 2-decyloxy-5- (p-hydroxyphenyl) pyrimidine and 0.2 g of 4-pyrrolidinopyridine in 20 ml of dry dichloromethane. 2.5 g (12 mmol) of dicyclohexylcarbodiimide was added, and the mixture was stirred at room temperature for 6 hours. After the reaction,
After adding 5% acetic acid aqueous solution and extracting with dichloromethane, the organic layer is sequentially washed with water and a 7% aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is purified by silica gel column chromatography. And optically active (+)-4- (1-hexyloxy-2,2,
5.05 g of 2-trifluoroethyl) benzoic acid 2-decyloxy-5- (p-hydroxyphenyl) pyrimidine
(82% yield).

Example 5 The compounds shown in Table 1 can be synthesized in the same manner as in the above example.

[0022]

[Table 1]

[0023]

[Table 2]

Using the liquid crystal compound of the present invention, a liquid crystal composition shown in Table 2 was 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.

[0025]

[Table 3]

<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 rubbed in a certain direction so that the rubbing directions of the two substrates are parallel. Glass fiber (diameter 2μ)
Using m) as a spacer, a liquid crystal cell was assembled, and the above liquid crystal composition was vacuum-sealed therein to obtain a liquid crystal element. This liquid crystal element was combined with a polarizer, an electric field of 20 V was applied, and the change in transmitted light intensity was observed. As a result, it became clear that the switching element was used.

The following compounds of the present invention (compounds of Example 1)
2 shows the spontaneous polarization and the phase series of the compound and a comparative compound. The compound of Example 1 shows a value that is at least twice as large as that of the comparative compound in spontaneous polarization while being monotropic.

[0028]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Chizu Sekine 6 Kitahara, Tsukuba, Ibaraki Pref. Within Sumitomo Chemical Co., Ltd. (72) Inventor Takeshi Tani 6 within Kitahara, Tsukuba, Ibaraki Pref. Sumitomo Chemical Co., Ltd. (72) Inventor Koichi Fujisawa 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. (56) References JP-A-3-31243 (JP, A) JP-A-3-294246 (JP, A) (58) (Int.Cl. ⁷ , DB name) C07D 239/34 C07D 239/26 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The general formula 1 (Wherein, R represents a fluoroalkyl group having 1 or 2 carbon atoms, R ¹ represents an alkyl group having 1-15 carbon atoms, and R ² represents an alkyl group having 1-15 carbon atoms which may be substituted with a halogen atom. A group or an alkoxyalkyl group having 2 to 15 carbon atoms, Y represents -O-, -COO- or -OCO-, and A represents Wherein X represents a hydrogen atom or a halogen atom. m and s each represent 0 or 1. * Indicates an asymmetric carbon atom. ) An optically active pyrimidine compound represented by the formula: 2. The general formula 2 (Wherein, R ¹ , A, X, Y and m have the same meanings as described above) and a phenol derivative represented by the following general formula: (Wherein, Z represents a halogen atom or a hydroxyl group; R, R
² , s and * have the same meaning as described above. 2. The method for producing an optically active pyrimidine compound according to claim 1, wherein an optically active carboxylic acid represented by the formula (1) is reacted. 3. A liquid crystal composition comprising at least one optically active pyrimidine compound according to claim 1. 4. A liquid crystal device comprising a liquid crystal composition containing at least one optically active pyrimidine compound according to claim 1.