JP2946891B2 - Optically active nitrile derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organic compound and a method for producing the same, and more particularly, to an optically active nitrile derivative useful as a compounding component of a ferroelectric liquid crystal composition and a method for producing 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, may have a remarkable improvement in response speed (Clark et al .; Applied. Phy).
s. 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 characteristics are required for the ferroelectric liquid crystal material used in the ferroelectric liquid crystal element actually used,
At present, a single compound cannot satisfy these requirements, and it is necessary to use a ferroelectric liquid crystal composition obtained by mixing several liquid crystal compounds or non-liquid crystal compounds. Further, not only a ferroelectric liquid crystal composition comprising only a ferroelectric liquid crystal compound but also a liquid crystal composition disclosed in JP-A-61-195187.
In the publication, non-chiral smectic C, F, G, H,
A compound or a composition exhibiting a phase such as I (hereinafter, abbreviated as a phase such as Sc) 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 obtain a ferroelectric substance It is reported that it can be obtained as a 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. Cryst. Liq.
Cryst., 89, 327 (1982)). Taken together, it can be seen that a ferroelectric liquid crystal composition can be constructed 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.

[0003]

It is desired to develop a compound having a sufficient spontaneous polarization, capable of high-speed response, and capable of forming a ferroelectric liquid crystal composition exhibiting a ferroelectric liquid crystal phase in a temperature region near room temperature. It is rare.

[0004]

SUMMARY OF THE INVENTION The present invention is useful as a component of 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. A novel optically active nitrile derivative and a method for producing the same are provided. That is, the present invention provides a compound represented by the general formula 1 (Wherein, R represents an alkyl group which may be substituted with a halogen atom having 1 to 15 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms, and X represents -COO- or -OCO-
Is the formula Is shown. Here, m and n represent 1 or 2, respectively, and s
Represents 0 or 1, p represents an integer of 0 to 6, q represents an integer of 1 to 6, and * represents an asymmetric carbon atom. ) And a method for producing the same.

Hereinafter, the present invention will be described in detail. The compound of the present invention wherein X is -COO- in the optically active nitrile derivative (Chemical Formula 1) can be produced by the following method. That is, the general formula (Formula 2) (Wherein m represents 1 or 2, and Y represents a halogen atom or a hydroxyl group) and a carboxylic acid derivative represented by the general formula:
Chemical 3 (Wherein, R, Z, n and s have the same meanings as described above). Here, as the substituent R of the optically active phenols represented by the general formula 3 and the optically active nitrile derivative represented by the general formula 1,
Specific examples 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, 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 Octyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyl Shiechiru, pentyloxy propyl, pentyl oxy butyl, pentyl oxy pentyl,
Pentyloxyhexyl, pentyloxyheptyl, pentyloxyoctyl, pentyloxynonyl, pentyloxydecyl, pentyloxymethyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyheptyl, pentyloxy Octyl, pentyloxynonyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, hexyloxyheptyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, Heptyloxymethyl,
Heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxymethyl, octyloxyethyl, octyloxypropyl, octyloxybutyl, octyloxypentyl, nonyloxymethyl, nonyloxyethyl, nonyloxypropyl, nonyloxy Butyl, 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, -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, 2,4-dihalopentyl, 2,4-dihalopentyl, 2,5-dihalopentyl, 2-halo3
2-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 (however, halo in the above alkyl group means fluorine, chlorine, bromine or iodine) .

For the reaction between the optically active phenols (Chemical Formula 3) and the carboxylic acid derivative (Chemical Formula 2), a usual esterification method can be applied, and a catalyst or condensation is carried out in the presence or absence of a solvent. The reaction can be carried out by using an agent. When a solvent is used in this reaction, examples of the solvent include tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane and pyridine. Solvents which are inert to the reaction, such as aliphatic or aromatic hydrocarbons, ethers, halogenated hydrocarbons, and organic amines, alone or in a mixture. The amount of such a solvent can be used without any particular limitation.

In this reaction, the optically active phenol (Chemical Formula 3) is relatively expensive, so that the carboxylic acid derivative (Chemical Formula 2), which is the other raw material, is used in an excessive amount in order to use it effectively. The reaction is preferably carried out using 1 to 4 equivalents, preferably 1 to 2 equivalents. When a catalyst is used, examples of the 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 or 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. The substance is used.

Further, when the carboxylic acid derivative (formula 2) is a carboxylic acid, carbodiimides such as N, N'-dicyclohexylcarbodiimide and N-cyclohexyl-N '-(4-diethylamino) cyclohexylcarbodiimide are condensed. It is preferably used as an agent, 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 with respect to the carboxylic acid derivative (Chemical Formula 2). When an organic base is used in combination, the amount of the organic base used is 0 to the condensing agent. 0.01 to 0.2 equivalent times.

The reaction temperature in the reaction between an optically active phenol (Chemical Formula 3) and a carboxylic acid 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 phenol compound 3 as a raw material. After the completion of the reaction, the desired optically active nitrile derivative represented by the general formula 1 (X = -COO-) is isolated from the reaction mixture by a usual separation means such as extraction, liquid separation, concentration and the like. It can be purified by column chromatography, recrystallization, etc., if necessary.

Next, the compound of the optically active nitrile derivative (formula 1) of the present invention wherein X is -OCO- can be produced by the following method. That is,
General formula 4 (Wherein m represents the same meaning as described above) and a phenol derivative represented by the general formula (Wherein, Y ′ represents a halogen atom or a hydroxyl group;
Z, n and s have the same meaning as described above. )) Can be obtained by reacting an optically active carboxylic acid represented by the formula (1).

The substituent R of the optically active carboxylic acid represented by the general formula (5) and the optically active nitrile derivative represented by the general formula (1) include the above-mentioned substituents.

For the reaction between the optically active carboxylic acid (Chemical Formula 5) and the phenol derivative (Chemical Formula 4), 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 The reaction can be carried out according to the reaction between the carboxylic acid derivative (Chemical Formula 2) and the optically active phenols (Chemical Formula 3).

By the above-described production method, an optically active nitrile derivative (formula 1) can be obtained. When this derivative is used as a component of a liquid crystal, particularly, a component of a ferroelectric liquid crystal, a general formula is used. It is preferred that the substituent R in 1 is an alkyl group or an alkoxyalkyl group containing no halogen atom. When the compound of the present invention is used as a liquid crystal composition, it contains at least one optically active nitrile derivative represented by the above general formula 1 as a compounding component, and the liquid crystal composition is an optically active nitrile derivative (chemical formula 1) 0.1 to 99.9% by weight of the obtained liquid crystal composition,
Preferably, it is contained in an amount of 1 to 99% by weight. 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. .

[0015]

The optically active nitrile derivative (formula 1) of the present invention has very excellent properties as a liquid crystal compound, and is effective as a component for improving the alignment of a liquid crystal composition and improving contrast. Can be used for Due to the above excellent properties, the optically active nitrile derivative (formula 1) of the present invention can be effectively used as a liquid crystal composition and further as a liquid crystal element using the same. Furthermore, according to the method of the present invention, an optically active nitrile derivative (formula 1) can be easily obtained at a high yield, which is industrially advantageous.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 (Compound of No. 8) Optically active (+)-4- (1-hexyloxyethyl)
2.5 g (0.01 mol) of benzoic acid, p-cyanophenol 1.
19 g (0.01 mol) and 0.1 g of 4-pyrrolidinopyridine were dissolved in 20 ml of dry dichloromethane, and 2.5 g (0.012 mol) of dicyclohexylcarbodiimide was added, followed by stirring 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 with water and a 7% aqueous sodium hydrogen carbonate solution successively, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Purified by chromatography and optically active (+)-4-
3.1 g (88% yield) of p-cyanophenyl (1-hexyloxyethyl) benzoate was obtained. Melting point: -50 ° C or less (colorless and transparent liquid at room temperature) [α] _D ²⁵ : + 20.5 ° (C = 1.1; chloroform)

Example 2 (Compound of No. 1) Optically active (+)-4- (1-hexyloxyethyl)
2.2 g (0.01 mol) of phenol and 1.6 g (0.01 mol) of p-cyanobenzoic acid chloride in 20 ml of dried pyridine
And stirred at room temperature for 6 hours. After completion of the reaction, 4N hydrochloric acid was added, and the mixture was extracted with dichloromethane. The organic layer was washed successively with water and a 7% aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Purified optically active p
3.2 g (yield 89%) of (+)-4- (1-hexyloxyethyl) phenyl cyanobenzoate was obtained. Melting point: 60-61 ° C [α] _D ²⁵ : + 15.8 ° C (C = 1.2; chloroform)

Example 3 (Compound No. 40) Optically active (+)-4- (1-hexyloxyethyl)
-4'-biphenylcarboxylic acid 3.0 g (0.01 mol), p
-1.2 g (0.01 mol) of cyanophenol and 0.1 g of 4-pyrrolidinopyridine are dissolved in 20 ml of dry dichloromethane, and 2.5 g of dicyclohexylcarbodiimide (0.01 g) is dissolved.
2 mol) and 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. (+)-4- (1-hexyloxyethyl)-
3.6 g of p'-cyanophenyl 4'-biphenylcarboxylate
(91% yield). [Α] _D ²⁵ : + 12.8 ° (C = 1.0; chloroform)

Example 4 (Compound of No. 29) Optically active (+)-4- (1-hexyloxyethyl)
2.5 g (0.01 mol) of benzoic acid, 2.0 g (0.01 mol) of 4-cyano-4'-hydroxybiphenyl, and 0.1 g of 4-pyrrolidinopyridine were dissolved in 20 ml of dry dichloromethane, and 2.5 g (0.012 mol) of dicyclohexylcarbodiimide was dissolved.
Mol) and stirred at room temperature for 6 hours. After the reaction is completed, 5
% Aqueous acetic acid and extracted with dichloromethane. The organic layer was washed successively with water and a 7% aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, evaporated, and purified by silica gel column chromatography. 3.6 g (91% yield) of 4-cyano-biphenylyl optically active (+)-4- (1-hexyloxyethyl) benzoate was obtained. [Α] _D ²⁵ : + 11.8 ° (C = 1.5; chloroform)

Example 5 By reacting in the same manner as described above, an optically active nitrile derivative represented by the following general formula 1 can be obtained.

[0021]

[Table 1]

[0022]

[Table 2]

REFERENCE EXAMPLE 1 The compound of the present invention No. 8 was added with 5 mol%, A composition consisting of 95 mol% of the compound represented by the formula was prepared. This composition was a liquid crystal composition showing a chiral smectic C phase at room temperature. This composition is sandwiched between two glass substrates, each having a transparent electrode and a polyimide alignment film coated on a glass substrate, with a gap of 2 μm using a spacer, and polarized light is applied to the outside of each of the two glass substrates. Two polarizing plates were placed in a state where the plane was rotated by 90 °, and a liquid crystal element was prepared. At this time, the polarization axis on the light incident side was set so as to coincide with the rubbing direction of the polyimide alignment film.
The contrast ratio was measured using this liquid crystal element. The contrast ratio was obtained by measuring the intensity of the emitted light when a light was incident on the liquid crystal element and applying a rectangular wave of ± 20 V with a photomultiplier, and determining the intensity ratio between the light in the dark state and the light in the bright state. The contrast ratio of this composition was 26. The contrast ratio of each compound alone was 3 or less.

Reference Example 2 A composition comprising 10 mol% of the compound No. 8 of the present invention and 90 mol% of the compound represented by the formula 6 was prepared. This composition was a liquid crystal composition showing a chiral smectic C phase at room temperature. The contrast ratio of this composition was measured in the same manner as in Reference Example 1. The contrast ratio was 52.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The general formula 1 (Wherein, R represents an alkyl group which may be substituted with a halogen atom having 1 to 15 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms, and X represents -COO- or -OCO-
Is the formula Is shown. Here, m and n represent 1 or 2, respectively, and s
Represents 0 or 1, p represents an integer of 0 to 6, q represents an integer of 1 to 6, and * represents an asymmetric carbon atom. ) An optically active nitrile derivative represented by the formula: 2. The general formula 2 (Wherein, m represents the same meaning as described above, and Y represents a halogen atom or a hydroxyl group) and a carboxylic acid derivative represented by the following general formula: (Wherein R, Z, n and s have the same meanings as described above), and are reacted with an optically active phenol represented by the general formula (1).
A method for producing an optically active nitrile derivative wherein is -COO-. 3. The general formula (Wherein m represents the same meaning as described above) and a phenol derivative represented by the general formula (Wherein, Y ′ represents a halogen atom or a hydroxyl group;
Z, n and s have the same meaning as described above. The method for producing an optically active nitrile derivative of the general formula (1), wherein X is -OCO-, characterized by reacting an optically active carboxylic acid represented by the formula (1).