JPH0699413B2 - Liquid crystalline compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel liquid crystal compound used for a display device or an electro-optical device.

(Prior Art) Liquid crystal has been widely used as a display material, but at present, TN (Twisted Nemati) is used as a display method.
c) Type is generally adopted. This TN type display system has the advantages that it consumes less power, and that it is a light receiving type that does not cause eye strain, but its drive is basically based on the anisotropy of the relative permittivity, and its power is weak. Due to its slow speed, it has been limited in applications to fields requiring high-speed response.

Ferroelectric liquid crystals were first discovered by RB Meyer in 1975 (J. Physi-que, 36, L-69 (197
5)), this has an excellent performance that the response speed is extremely fast because it has a relatively large force derived from spontaneous polarization as the driving force, and it has a memory property, and is attracting attention as a new display element.

As a condition for the liquid crystal to exhibit ferroelectricity, it is necessary to exhibit a chiral smectic C phase (SmC ^* phase), and therefore an asymmetric carbon must be contained in the molecule. Also, it is necessary to have a dipole moment perpendicular to the long axis of the molecule.

The ferroelectric liquid crystal DOBAMBC synthesized by Meyer et al. Has the following structure. Although the above conditions were satisfied, it was chemically unstable because it contained a Schiff base, and the spontaneous polarization was as small as 3 × 10 ^-9 C / cm ² . After that, many ferroelectric liquid crystal compounds have been synthesized, but none of them have been found to respond sufficiently fast, and thus have not been put to practical use.

When comparing these conventional ferroelectric liquid crystal compounds, for example, DOBA-1-MBC in which one asymmetric carbon atom of DOBAMBC is closer to the carbonyl group Shows that the spontaneous polarization is 5 × 10 ^-8 C / cm ² , which is larger than DOBAMBC. It is thought that this is because the asymmetric carbon, which is an important factor for the emergence of ferroelectricity, and the position of the dipole were brought closer to each other, so that the free rotation of the dipole part of the molecule was suppressed and the orientation of the dipole was improved. To be That is, the asymmetric portion functions to constrain the free rotation of the molecule, and since most conventional ferroelectric liquid crystal compounds have the asymmetric portion on a straight chain,
It is considered that satisfactory spontaneous polarization and high-speed response could not be obtained because the free rotation of the molecule could not be completely suppressed and the dipole part could not be fixed.

(Problems to be Solved by the Invention) As a result of intensive research to obtain a ferroelectric liquid crystal compound without the above-mentioned problems, the present inventors have aimed to suppress the free rotation of the dipole portion of a conventional ferroelectric liquid crystal compound. A novel ferroelectric liquid crystal compound having an optically active γ-lactone ring, which is constrained from free rotation and has a chemically stable structure, is formed by directly connecting an asymmetric part to a 5-membered ring lactone. I found it.

(Means for Solving the Problems) The present invention provides the following general formula (A): (In formula (A), R ¹ is Wherein n is 0 or 1, R ³ is a linear or branched alkyl group having 5 to 10 carbon atoms, R ² is a linear or branched alkyl group having 1 to 5 carbon atoms, and * Is a liquid crystal compound having an optically active γ-lactone ring and its racemic compound.

In the general formula A, the alkyl group of R ² and R ³ is, for example, R ² , such as methyl, ethyl, n-propyl, n.
-Butyl, n-pentyl, isopropyl, t-butyl, 2-methylpropyl, 1-methylpropyl, 3-methylbutyl, 2-
Examples thereof include groups such as methylbutyl and 1-methylbutyl, and examples of R ³ include n-pentyl, n-hexyl, n-
Heptyl, n-octyl, n-nonyl, n-decyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 5-methylhexyl , 4-methylhexyl, 3-
Methylhexyl, 2-methylhexyl, 1-methylhexyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 7-methyloctyl, 6- Methyloctyl, 5-
Methyloctyl, 4-methyloctyl, 3-methyloctyl, 2-methyloctyl, 1-methyloctyl, 8-methylnonyl, 7-methylnonyl, 6-methylnonyl, 5-methylnonyl, 4-methylnonyl, 3-methylnonyl, 2-methylnonyl, Examples thereof include groups such as 1-methylnonyl.

The novel compound according to the present invention has a carbonyl group as a part having a dipole moment for generating ferroelectricity, which is located inside a 5-membered ring, and further has two asymmetric carbons on the ring. As a result, free rotation of this portion is disabled, the dipole portion can be oriented in one direction as a whole, the spontaneous polarization can be increased, and a high-speed response can be realized. In addition, since the fluorine atom is substituted on the benzene ring of R ^{1 in} the formula (A), the melting point is lower than that of the compound having no fluorine atom, and the chiral smectic C
The temperature range of the (SmC ^* ) phase can be expanded to the low temperature side, the tilt angle can be increased, and the spontaneous polarization can be increased. Further, since the compound of the general formula (A) contains two asymmetric carbon atoms in the γ-lactone ring, there are two kinds of diastereomers. Since all of them have a structure that meets the purpose of suppressing the free rotation of the dipole portion, they are useful as a liquid crystal compound either individually or as a mixture thereof.

Further, in the present invention, the above-mentioned liquid crystalline compound includes not only a substance whose liquid crystal state can be observed alone, but also a compound which is useful as a constituent component of a liquid crystal composition even if it does not exhibit a liquid crystal phase itself.

The compound represented by the general formula (A) according to the present invention can be produced by the following method.

That is, the following general formula (B), (The symbols R ¹ and * in the formula (B) have the same meanings as the symbols R ¹ and * in the formula (A)), an optically active glycidyl ether represented by the following formula (C), (Formula (C) Medium R ² represent the same meaning as R ² in formula (A),
R ⁴ represents a lower alkyl group) and a malonic ester derivative represented by the formula (4) can be produced by adding a base in an organic solvent and reacting.

The above-mentioned compound of the formula (A) is produced by refluxing the compound of the formula (B) and 1 to 5 equivalents of the compound of formula (C) with 1 to 5 equivalents of a base in an organic solvent for 1.5 to 24 hours. . As the base used at this time, sodium methoxide, sodium ethoxide, potassium t-butoxide or sodium hydride, lithium hydride or n-
Butyl lithium and the like are preferable, and as the organic solvent, alcohols such as methanol, ethanol and t-butyl alcohol, tetrahydrofuran, ethyl ether, dimethoxyethane, diethylene glycol dimethyl ether,
Ethers such as dioxane, aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, and mixed solvents thereof are preferable.

The optically active glycidyl ether of formula (B), which is the above-mentioned raw material compound, can be produced by the following method.

(Code wherein R ¹ and * are the formula (which has the same meaning as R ¹ and * the sign of A)) reacting an optically active epichlorohydrin in the presence of a base to phenol derivatives represented by the R ¹ OH Obtained by The optically active epichlorohydrin is preferably 1 to 10 equivalents based on the starting phenol derivative, and the base used in the reaction is preferably 1 to 5 equivalents based on the starting phenol derivative. Examples of the base include sodium hydroxide, potassium hydroxide, potassium t-butoxide and the like.
The reaction proceeds smoothly without a catalyst, but quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and 4- (N, N-dimethylamino) pyridine. It is also possible to add the catalyst of 0.01 to 0.1 equivalent to the starting phenol derivative. Although it is possible to react with optically active epichlorohydrin as a solvent,
If necessary, polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, acetonitrile, t-butyl alcohol and water can be used. The reaction is completed in 0.5 to 60 hours at a temperature of 20 to 80 ° C.

As another method different from the above method, the raw material phenol derivative and the optically active epichlorohydrin are reacted as a base in the presence of 0.1 to 0.5 equivalents of an amine, for example, morpholine, piperidine, pyridine, etc., relative to the phenol derivative to obtain optically active chlorohydrin. 1 to 5 equivalents of a base, for example, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium t-butoxide, etc. are reacted to obtain a glycidyl ether by ring closure. Although this method is a two-step reaction, it has an advantage that the extraction operation is easy. In this case, the reaction is 50-80 ℃,
It ends in 24 hours.

A racemic glycidyl ether can be obtained by using a racemic epichlorohydrin. The optically active epichlorohydrin used as the raw material has a high purity, and the R-isomer is the R-form of the present applicant.
As the method described in JP-A No. 6 and JP-A-62-6697, and as the S-form, those obtained by the method described in JP-A 1-230567 can be used.

The starting phenol derivative (R ¹ OH) used for producing the compound of the formula (B) can be synthesized as follows.

However, in the following Table 1, R ³ and n have the same meaning as R ³ and n in the formula (A), X is a chlorine atom or a bromine atom,
Ph represents a phenyl group.

Explaining the synthesis method of Table 1, compound (I) in which the hydroxyl group of fluorine-substituted 4-bromophenol is protected with a benzyl group is reacted with magnesium to give a corresponding Grignard reagent, and then in the presence of palladium chloride. Cross-coupling reaction of 4-alkyliodobenzene (II) obtained by iodine substitution of alkylbenzene with iodine and periodic acid is carried out to obtain the corresponding biphenyl derivative (IV). Then, this is Pd-C
Fluorine substitution by hydrogenolysis in the presence of a catalyst 4-
(4-Alkylphenyl) phenol (VI) can be synthesized.

On the other hand, instead of 4-alkyliodobenzene (II) in the synthesis of (IV) above, compound (III) in which the hydroxyl group of 4-iodophenol was alkylated with alkyl bromide was used, and (I) and (II ) Is used as a starting material in the same synthetic reaction step as (IV) to obtain the corresponding biphenyl derivative (V), which is subsequently reacted in the same manner as in the synthetic reaction step starting from (IV) above. By doing so, fluorine-substituted 4- (4-alkyloxyphenyl) phenol (VII) can be synthesized.

The liquid crystalline compound of the present invention can be obtained as a racemic compound by using racemic epichlorohydrin as a raw material.
This compound can be added to other optically active liquid crystal compounds and used for the preparation of its helical pitch. The liquid crystalline compound of the present invention has good stability against heat and light, and its optically active substance has excellent properties as a ferroelectric liquid crystal. The liquid crystalline compound of the present invention can also be used for the following applications.

(1) Addition to TN type and STN type liquid crystals to suppress the generation of reverse domains.

(2) Display device using cholesteric-nematic phase transition effect (JJ Wysoki, A. Adams and W. Haas; Phys. Re
v. Lett., 20 , 1024 (1968)).

(3) White Tiller type display device using guest-host effect (DLWhite and GNTaylor; J.Appl.Phys.,
45, 4718 (1974)).

(4) Immobilize the cholesteric phase in the matrix,
It is used as a notch filter or bandpass filter by utilizing its selective scattering property (FJKahn; Appl.Phys.Let
t., 18 , 231, (1971)).

(5) Circular polarization beam splitter (SDJacob, SPIE.37,98 (198) that uses the circular polarization characteristics of the cholesteric phase.
1)).

Hereinafter, the production of the compound according to the present invention and application examples using the compound will be specifically described by way of Examples, but the present invention is not limited to these Examples.

(Example) In each of the following examples, the optically active compound (A) of the present invention
The R and S indications were based on the position numbers in the chemical formula below.

Further, the phase transition temperatures described in the examples were determined by DSC and polarization microscope observation. The symbols shown in the section of the phase transition temperature represent the following phases.

C; Crystal phase SmA; Smectic A phase SmC ^* ; Chiral smectic C phase I; Isotropic liquid phase n-octylbenzene 38.06g, iodine 20.30g, periodic acid (dihydrate) 9.12g, glacial acetic acid 98ml, water 19ml and concentrated sulfuric acid 3ml
The mixture was stirred at 70 ° C. for 3 hours. After allowing to cool, water was added, and the mixture was extracted with hexane. The extract was washed with aqueous sodium carbonate solution, then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off and the obtained oily substance was distilled under reduced pressure to obtain 52.9 g of desired 4-n-octyliodobenzene.

bp 144 ° C / 2mmHg NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 7.0Hz) 1.2 to 1.4 (10H, m) 1.4 to 1.6 (2H, m) 2.53 (2H, t, J = 7.9Hz) 6.92 (2H, d, J = 8.2Hz) 7.57 (2H, d, J = 8.2Hz) Synthesis example 2 4-iodophenol (25 g) was dissolved in 100 ml of t-butyl alcohol, and potassium t-butoxide (14.01 g) was added to the solution.
Stir at ~ 45 ° C for 4 hours. The solution was ice-cooled, 24.14 g of n-octyl bromide was gradually added, and the mixture was further stirred for 3 hours at room temperature. The solvent was distilled off from the mixture under reduced pressure, water was added to the residue, and the mixture was extracted with chloroform. The crude product obtained from the extract was purified by silica gel column chromatography, and the chloroform eluate was distilled under reduced pressure to obtain 12 g of desired 4- (n-octyloxy) iodobenzene.

bp 163 ° C./3 mmHg NMR (CDCl ₃ ) δ: 0.88 (3H, t) 1.2 to 1.5 (10H, m) 3.90 (2H, t) 6.65 (2H, d) 7.52 (2H, d) Synthesis Example 3 4-bromo-2-fluorophenol 25g, potassium carbonate
A mixture of 19 g and 100 ml of acetone was stirred under reflux for 30 minutes.
After allowing to cool, 17.40 g of benzyl chloride was added dropwise at room temperature over 15 minutes. After stirring under reflux for 7 hours, the solid was separated, acetone was distilled off from the solution under reduced pressure, water was added to the residue, the mixture was extracted with chloroform, the extract was washed, dried and purified by silica gel column chromatography. The chloroform eluate was distilled under reduced pressure to obtain 22.24 g of the target benzyl (4-bromo-2-fluorophenyl) ether.

bp 143 ° C./2 mmHg NMR (CDCl ₃ ) δ: 5.12 (2H, s) 6.8 to 7.4 (8H, m) Synthesis Example 4 Formula (IV) To a 200 ml three-necked flask equipped with a magnetic stirrer, a Liebig condenser, a nitrogen gas inlet tube and a dropping funnel, 2.07 g of magnesium scrap and 10 ml of dry tetrahydrofuran were placed, and the benzyl obtained in Synthesis Example 3 was added to the dropping funnel. 4-bromo-2-fluorophenyl ether
8 g of 15 ml dry tetrahydrofuran solution was added. Under a nitrogen stream, the above solution was added dropwise little by little and the flask was heated, and the whole amount was added dropwise in 30 minutes while gradually reacting. The mixture was stirred at reflux for an additional 2 hours. Subsequently, 13.47 g of 4-n-octyliodobenzene obtained in Synthesis Example 1, 100 mg of palladium chloride, 50 mg of iodine and dry tetrahydrofuran.
The above reaction solution was added dropwise to a 200 ml three-necked flask containing 50 ml and stirred under a nitrogen stream in 40 minutes, and after the completion, the mixture was stirred under reflux for 2 hours. After cooling, 10% hydrochloric acid was added to acidify the liquid property of the mixture, water was added, and the mixture was filtered through Hyflo Supercel and extracted with ether from the liquid. After washing and drying the extract, the ether was distilled off from the extract to purify the crude product, which was purified by silica gel column chromatography. The colorless solid obtained from the elution of carbon tetrachloride was recrystallized from hexane. Target benzyl 4- (4'-n-octylphenyl)
There was obtained 3.47 g of 2-fluorophenyl ether.

mp 98 ° C NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.7Hz) 1.2 to 1.4 (10H, m) 1.55 to 1.7 (2H, m) 2.62 (2H, t, J = 7.7Hz) 5.17 ( 2H, s) 7.0-7.4 (2H, m) Synthesis example 5 14.06 g of benzyl 4-bromo-2-fluorophenyl ether obtained in Synthesis Example 3 and 1.
The same procedure as in Synthesis Example 4 was repeated except that 22 g was used and 11.61 g of 4-n-octyloxyiodobenzene obtained in Synthesis Example 2 was used instead of 4-n-octyliodobenzene. -(4'-n-octyloxyphenyl) -2-fluorophenyl ether 5.6g
Got

mp 100 ° C NMR (CDCl ₃ ) δ: 0.89 (3H, t, J = 7.0Hz) 1.2 to 1.6 (10H, m) 1.7 to 1.8 (2H, m) 3.98 (2H, t, J = 6.6Hz) 5.17 ( 2H, s) 6.9 to 7.5 (12H, m) <Synthesis of phenol derivative> Synthesis example 6 Benzyl 4- (4'-n-octylphenyl) -2-fluorophenyl ether obtained in Synthesis Example 4 3.38 g, 5% P
A mixture of 2 g of dC (containing 52% water) and 200 ml of ethyl acetate was shaken under a hydrogen atmosphere at room temperature and 2 kg / cm ² for 3 hours. After the end,
The solid was separated, the solvent was distilled off from the liquid, and the obtained solid was recrystallized from benzene-hexane to give the desired 4- (4'-
n-octylphenyl) -2-fluorophenol 2.51
got g.

mp 99 ° C NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.7Hz) 1.2 to 1.4 (10H, m) 1.56 to 1.66 (2H, m) 2.63 (2H, t, J = 7.7Hz) 5.12 ( 1H, d, J = 4.2Hz) 7.0 to 7.4 (7H, m) IR (KBr) 3424cm ^-1 (ν _OH ) Synthesis example 7 Benzyl 4- (4'-n-octyloxyphenyl) -2-fluorophenyl ether obtained in Synthesis Example 5 5 g, 5
A mixture of 2.5 g of Pd-C (52% water content) and 200 ml of ethyl acetate was reacted and treated in the same manner as in Synthesis Example 6 to obtain the desired 4- (4'-
3.71 g of n-octyloxyphenyl) -2-fluorophenol was obtained.

mp 115.5 ° C NMR (CDCl ₃ ) δ: 0.89 (3H, t, J = 6.8Hz) 1.2 to 1.5 (10H, m) 1.7 to 1.85 (2H, m) 3.98 (2H, t, J = 6.6Hz) 5.18 ( 1H, d, J = 3.9Hz) 6.9 to 7.4 (7H, m) IR (KBr) 3544cm ^-1 (ν _OH ) <Synthesis of compound of formula (B)> As a starting optically active epichlorohydrin, the applicant of the present invention Those manufactured by the methods described in JP-A-61-132196 and JP-A-62-6697 were used. These substances are R-(-)-epichlorohydrin and have a chemical purity of 98.5% or more and an optical purity of 99% or more by gas chromatography analysis (specific optical rotation is ▲ [α] ²⁵ _D ▼ -34.0 °, C = 1.2%. , Methanol).

Synthesis example 8 A solution of 2.38 g of 4- (4'-n-octylphenyl) -2-fluorophenol obtained in Synthesis Example 6 and 80 ml of t-butyl alcohol was added to potassium t-butoxide.
1.06 g was added, followed by R-(-)-epichlorohydrin
3.1 ml and 4- (N, N-dimethylamino) pyridine 50 mg
Was added and the mixture was stirred at 40 ° C for 1 day. The mixture was concentrated under reduced pressure, water was added to the residue, and the mixture was extracted with chloroform. The extract was washed and dried, and then the chloroform was distilled off to obtain a crude product, which was purified by silica gel column chromatography.
2.22 g of body glycidyl ether was obtained.

mp 59 ° C ▲ [α] ²¹ _D ▼ ＋ 4.66 ° (C = 1.04, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.5Hz) 1.2 to 1.4 (10H, m) 1.54 to 1.7 (2H, m) 2.63 (2H, t, J = 7.7Hz) 2.78 (1H, dd, J = 2.7, 4.9Hz) 2.92 (1H, t, J = 4.8Hz) 3.35 to 3.45 (1H, m ) 4.08 (1H, dd, J = 5.7, 11.4Hz) 4.32 (1H, dd, J = 3.3, 11.4Hz) 7.0 to 7.45 (7H, m) MS (EI) 3m / z 356 (M ⁺ ) Synthesis example 9 4- as the raw material phenol derivative obtained in Synthesis Example 7
(4'-n-octyloxyphenyl) -2-fluorophenol 2.68 g, potassium t-butoxide 1.12 g, R-
(−)-Epichlorohydrin 3.3 ml, 4- (N, N-dimethylamino) pyridine 50 mg and t-butyl alcohol 60 ml were used to carry out the same reaction and treatment as in Synthesis Example 8 to obtain S represented by the following chemical formula. 2.17 g of body glycidyl ether was obtained.

mp 96 ° C ▲ [α] ²² _D ▼ ＋ 4.65 ° (C = 1.00, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.89 (3H, t, J = 6.8Hz) 1.2 to 1.55 (10H, m) 1.74 to 1.85 (2H, m) 2.78 (1H, dd, J = 2.8, 5.0Hz) 2.91 (1H, t, J = 5.0Hz) 3.35 to 3.42 (1H, m) 3.98 (2H, t, J = 6.6Hz ) 4.08 (1H, dd, J = 5.5, 11.3Hz) 4.31 (1H, dd, J = 3.3, 11.3Hz) 6.9 to 7.45 (7H, m) MS (EI) 3m / z 372 (M ⁺ ) <Equation ( A) Synthesis of Compound> Example 1 S-form glycidyl ether obtained in Synthesis Example 8 600 mg, dimethyl methylmalonate 44 mg, potassium t-butoxide 264
mg and 10 ml of t-butyl alcohol were mixed and stirred under reflux for 1 hour. The reaction solution was returned to room temperature, water was added, and the pH was adjusted to 3 with 2N hydrochloric acid.
After that, the precipitated solid was collected, washed with water and dried. This product was separated and purified by silica gel column chromatography followed by normal phase silica gel high performance liquid chromatography to obtain the (2S, 4S) form 2 of the γ-lactone derivative represented by the following formula.
33 mg and (2R, 4S) body 136 mg were obtained.

(2S, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 21.06 ° (C = 1.01, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.6Hz) 1.2 to 1.4 (13H, m) 1.58 to 1.7 (2H, m) 1.8 to 2.0 (1H, m) 2.5 to 2.65 (3H, m) 2.69 to 2.81 (1H, m) 4.18 to 4.3 (2H, m) 4.7 to 4.8 (1H, m) 7.0 to 7.5 (7H , m) IR (KBr) 1782cm ^-1 (ν _c = 0) MS (EI) m / z 412 (M ⁺ ) (2R, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 27.00 ° (C = 1.02, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.6Hz) 1.1〜1.2 (13H, m) 1.55〜1.65 (2H, m) 2.06 to 2.18 (1H, m) 2.53 to 2.66 (3H, m) 2.93 to 3.06 (1H, m) 4.16 (1H, dd, J = 3.4, 10.4Hz) 4.28 (1H, dd, J = 3.5, 10.4Hz) 4.79 to 4.86 (1H, m) 6.96 to 7.44 (7H, m) IR (KBr) 1770cm ^-1 (ν _c = 0) MS (EI) m / z 412 (M ⁺ ) Example 2 S-form glycidyl ether obtained in Synthesis Example 8 700 mg, n
-Diethyl propylmalonate (596 mg), potassium t-butoxide (309 mg) and t-butyl alcohol (20 ml) were mixed, and mixed.
The mixture was stirred under reflux for hours. The treatment after the reaction is carried out in the same manner as in Example 1 to obtain (2S, 4) of the γ-lactone derivative represented by the following formula.
165 mg of (S) form and 237 mg of (2R, 4S) form were obtained.

(2S, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 38.17 ° (C = 1.00, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.7Hz) 0.97 (3H, t, J = 7.1Hz) 1.2 to 1.7 (15H, m) 1.9 to 2.0 (2H, m) 2.5 to 2.75 (4H, m) 4.18 to 4.3 (2H, m) 4.7 to 4.8 (1H, m) 7.0 to 7.5 (7H, m) IR ( KBr) 1766cm ^-1 (ν _c = 0) MS (EI) m / z 440 (M ⁺ ) (2R, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 24.76 ° (C = 1.02, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.7Hz) 0.98 (3H, t, J = 7.1Hz) 1.2 to 1.7 (15H, m) 1.8 to 2.0 (1H, m) 2.1 to 2.2 (1H, m) 2.4 to 2.6 (1H, m) 2.63 (2H, t, J = 7.7Hz) 2.85 to 3.0 (1H, m ) 4.16 (1H, dd, J = 3.5, 10.4Hz) 4.27 (1H, dd, J = 3.6, 10.4Hz) 4.8 to 4.86 (1H, m) 6.95 to 7.45 (7H, m) IR (KBr) 1768cm ^-1 (Ν _c = 0) MS (EI) m / z 440 (M ⁺ ) Example 3 S-form glycidyl ether obtained in Synthesis Example 9 650 mg, n
A mixture of 529 mg of diethyl propylmalonate, 274 mg of potassium t-butoxide and 20 ml of t-butyl alcohol was added to 1.5.
The mixture was stirred under reflux for hours. The treatment after the reaction is carried out in the same manner as in Example 1 to obtain (2S, 4) of the γ-lactone derivative represented by the following formula.
S) form 310 mg and (2R, 4S) form 102 mg were obtained.

(2S, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 38.35 ° (C = 1.02, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.89 (3H, t, J = 6.7Hz) 0.97 (3H, t, J = 7.1Hz) 1.2 to 1.6 (13H, m) 1.74 to 2.0 (4H, m) 2.45 to 2.6 (1H, m) 2.6 to 2.75 (1H, m) 3.99 (2H, t, J = 6.6Hz) 4.15 to 4.3 (2H, m) ) 4.7 to 4.8 (1H, m) 6.8 to 7.5 (7H, m) IR (KBr) 1764cm ^-1 (ν _c = 0) MS (EI) m / z 456 (M ⁺ ) (2R, 4S) body Phase transition temperature ▲ [α] ²¹ _D ▼ + 21.51 ° (C = 0.79, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.89 (3H, t, J = 6.8Hz) 0.98 (3H, t, J = 7.1Hz) 1.2 to 1.55 (13H, m) 1.75 to 1.9 (3H, m) 2.05 to 2.2 (1H, m) 2.45 to 2.56 (1H, m) 2.85 to 2.95 (1H, m) 3.99 (2H, t, J = 6.6Hz ) 4.15 (1H, dd, J = 3.5, 10.3Hz) 4.26 (1H, dd, J = 3.5, 10.3Hz) 4.75 ~ 4.85 (1H, m) 6.9 ~ 7.4 (7H, m) IR (KBr) 1770cm ^-1 (Ν _c = 0) MS (EI) m / z 456 (M ⁺ ) <Physical Properties of Liquid Crystal Composition Containing Formula (A) Compound> Application Example 1 γ-lactone represented by the following formula and obtained in Example 1. Derivative (2S, 4S) form And a compound represented by the following chemical formula (1) The composition in which and were mixed at a ratio of 1:19 (by weight) was found to have the following phase transition temperature by DSC measurement and observation with a polarizing microscope.

It was found that the (2S, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

In addition, as a result of measuring the response time of the above composition, it was found that this composition exhibits a high-speed response of 35 μsec (40 ° C.). The response speed was determined by enclosing the above composition in a cell having a thickness of 2 μm treated with an aligning agent and changing the transmitted light intensity when a voltage of V _pp = 20 V under orthogonal Nicols was applied.
A PET film was used as the spacer, a polyimide film was used as the aligning agent, and an ITO electrode was used as the electrode, and the rubbing directions were parallel.

Application Example 2 The (2R, 4S) form of the γ-lactone derivative represented by the following chemical formula obtained in Example 1 And the compound of formula (1) used in Application Example 1 at 1:19 (weight)
It was found from the DSC measurement and the observation with a polarization microscope that the composition mixed in the ratio of 1) had the following phase transition temperature.

It was found that the (2R, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

Further, the response time of the above composition was measured in the same manner as in Application Example 1, and it was found that this composition exhibited a high-speed response of 60 μsec (40 ° C.).

Application Example 3 (2S, 4S) form of the γ-lactone derivative represented by the following chemical formula, obtained in Example 2 And the compound of formula (1) used in Application Example 1 at 1:19 (weight)
It was found from the DSC measurement and the observation with a polarization microscope that the composition mixed in the ratio of 1) had the following phase transition temperature.

It was found that the (2R, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

Further, the response time of the above composition was measured in the same manner as in Application Example 1, and it was found that this composition exhibited a high-speed response of 30 μsec (40 ° C.).

Application Example 4 (2S, 4S) form of the γ-lactone derivative represented by the following chemical formula, obtained in Example 2 And the compound of formula (1) used in Application Example 1 at 1:19 (weight)
It was found from the DSC measurement and the observation with a polarization microscope that the composition mixed in the ratio of 1) had the following phase transition temperature.

It was found that the (2R, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

Further, the response time of the above composition was measured in the same manner as in Application Example 1, and it was found that this composition exhibited a high-speed response of 25 μsec (40 ° C.).

Application Example 5 (2S, 4S) form of the γ-lactone derivative represented by the following chemical formula, obtained in Example 3 And the compound of formula (1) used in Application Example 1 at 1:19 (weight)
It was found from the DSC measurement and the observation with a polarization microscope that the composition mixed in the ratio of 1) had the following phase transition temperature.

It was found that the (2R, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

Further, the response time of the above composition was measured in the same manner as in Application Example 1, and it was found that this composition exhibited a high-speed response of 25 μsec (40 ° C.).

Application Example 6 (2R, 4S) -form of the γ-lactone derivative represented by the following chemical formula, obtained in Example 3 And the compound of formula (1) used in Application Example 1 at 1:19 (weight)
It was found from the DSC measurement and the observation with a polarization microscope that the composition mixed in the ratio of 1) had the following phase transition temperature.

It was found that the (2R, 4S) form of the above optically active γ-lactone derivative does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds.

The response time of the above composition was measured in the same manner as in Application Example 1, and it was found that this composition exhibited a high-speed response of 45 μsec (40 ° C.).

(Effect of the Invention) The novel liquid crystalline compound according to the present invention has better stability to heat and light as compared with conventional liquid crystal materials, is chemically stable, and has excellent properties as a ferroelectric liquid crystal. The compound is useful as a liquid crystal material having an extremely fast response speed.

Claims (2)

[Claims] 1. A general formula (A) (In formula (A), R ¹ is Wherein n is 0 or 1, R ³ is a linear or branched alkyl group having 5 to 10 carbon atoms, R ² is a linear or branched alkyl group having 1 to 5 carbon atoms, and * Is a liquid crystal compound having an optically active γ-lactone ring. 2. The compound according to claim 1, wherein the liquid crystal compound is a racemate.