JPH0433315B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel liquid crystal composition used for display elements or electro-optical elements. (Prior art) Liquid crystals have come to be widely used as a display material, but TN is currently the only display method.
(Twisted Nematic) type is generally adopted. This TN type display system has the advantages of requiring less power consumption and being light-receiving type so it does not tire the eyes, but since the drive is basically based on the anisotropy of the dielectric constant, the force is weak and the response is weak. It has the disadvantage of slow speed, which limits its application to fields that require high-speed response. Ferroelectric liquid crystals were first discovered in 1975 by RB Meyer et al. (J.
Physique, 36 , L-69 (1975)), this display has excellent performance in that it has an extremely fast response speed and has memory properties because the driving force is a relatively large force derived from spontaneous polarization, and it is a new display. It is attracting attention as an element. In order for a liquid crystal to exhibit ferroelectricity, it must exhibit a chiral smectic C phase (SMC ^* phase), and for this reason it must contain asymmetric carbon in its molecules. It is also necessary to have a dipole moment in the direction perpendicular to the long axis of the molecule. Ferroelectric liquid crystal DOBAMBC synthesized by Meyer et al.
has the following structure Although it satisfies the above conditions, it is chemically unstable because it contains a Schiff base, and its spontaneous polarization is also 3×.
It was small at 10 ^-9 C/cm ² . Since then, many ferroelectric liquid crystal compounds have been synthesized, but no one has yet been found that responds sufficiently quickly, and therefore has not been put into practical use. Comparing these conventional ferroelectric liquid crystal compounds, for example, DOBA-1-
MBC Then, the spontaneous polarization is 5×10 ^-8 C/cm ² ,
It's getting bigger than DOBAMBC. this is,
It is thought that because the asymmetric carbon, which is an important element for the emergence of ferroelectricity, and the dipole are located close to each other, free rotation of the dipole part of the molecule is suppressed and the orientation of the dipole is improved. In other words, the asymmetric moiety functions to restrict the free rotation of the molecule, and since most conventional ferroelectric liquid crystal compounds have the asymmetric moiety on a straight chain, it is not possible to completely suppress the free rotation of the molecule. It is thought that this was because the dipole part could not be fixed and satisfactory spontaneous polarization and high-speed response could not be obtained. (Problems to be Solved by the Invention) As a result of intensive research in order to obtain a ferroelectric liquid crystal compound free from the above-mentioned problems, the present inventors have found that, in order to suppress the free rotation of the dipole portion of conventional ferroelectric liquid crystal compounds, As a means of achieving this, we created a novel ferroelectric liquid crystal compound with a chemically stable optically active γ-lactone ring that restrains free rotation by creating a structure in which the asymmetric moiety is directly connected to a 5-membered lactone ring. The present applicant has filed a separate application for this compound. The present invention provides a liquid crystal composition containing as one component this compound, and furthermore, a compound obtained by adding a specific substituent to this compound, and an electro-optical element using the composition. (Means for solving the problem) The present invention has the following general formula (A), (R ¹ in formula (A) is

[Formula] or , n or e is each independently 0 or 1,
^R3 is an alkyl group having 1 to 15 carbon atoms, X or Y is an atom or group selected from a hydrogen atom, a halogen atom, and a cyano group, ^R2 is (-CO-) ^mR4 , and m is 0 or 1 , R ⁴ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and the symbol * represents an asymmetric carbon atom). A characteristic liquid crystal composition and an electro-optical element using the composition. In the above general formula (A), examples of the alkyl groups for R ³ and R ⁴ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-
Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, isopropyl, t-butyl, 2-methylpropyl, 1-methylpropyl, 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-methylnomyl, 3-
Methylnonyl, 2-methylnonyl, 1-methylnonyl, 3,7-dimethyloctyl, 3,7,11-
Examples include groups such as trimethyldodecyl. The above novel compound according to the present invention has a carbonyl group as a part having a dipole moment for generating ferroelectricity located inside a five-membered ring, and further has one or two asymmetric carbon atoms on the ring. By providing this, free rotation of this part is made impossible, and the dipole part as a whole can be oriented in one direction, increasing spontaneous polarization and, in turn, realizing high-speed response. In addition, by substituting a halogen atom or a cyano group in the benzene ring of R ¹ in formula (A), the melting point of the compound is lowered, and the temperature range of the chiral smectate C (SmC ^* ) phase is expanded to the lower temperature side,
Furthermore, by increasing the tilt angle, it is possible to increase spontaneous polarization. Furthermore, negative dielectric anisotropy is necessary to drive a ferroelectric liquid crystal, and the introduction of a cyano group is useful in that it provides a compound with large negative dielectric anisotropy. Also, the above general formula
In the compound (A), when R ² is a hydrogen atom, there is only one type, but compounds where R ² is other than a hydrogen atom contain two asymmetric carbon atoms in the γ-lactone ring, so there are two types of dia Stereomers exist. All of these have structures that meet the purpose of suppressing the free rotation of the dipole portion, so they are useful as liquid crystal compounds whether used alone or as a mixture of each. Furthermore, in the present invention, the liquid crystal compound includes not only a substance whose liquid crystal state can be observed by itself, but also a compound that is useful as a constituent of a liquid crystal composition even if it does not itself exhibit a liquid crystal phase. The compound represented by general formula (A) according to the present invention can be produced by the following method. That is, general formula (B), (The signs of R ¹ and * in formula (B) are the signs of R ¹ and * in formula (A).
) and the general formula (C) or (D), (R ⁴ in formulas (C) and (D) is a hydrogen atom or a carbon atom 1
~15 alkyl groups, R ⁵ indicates lower alkyl groups)
It can be produced by reacting a β-ketoester derivative represented by the formula or a malonic acid ester derivative in an organic solvent by adding a base. When producing the above formula (A) and the compound, the formula (B) compound and 1 to 5 equivalents of the formula (C) compound or the formula (D) compound are mixed with 1 to 5 equivalents of a base and 1.5 to 24 This is achieved by refluxing for a period of time. The base used in this case is sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium hydride, lithium hydride or n-
Butyl lithium is preferred, and organic solvents include alcohols such as methanol, ethanol, and t-butyl alcohol, ethers such as tetrahydrofuran, ethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, and dioxane, dimethylformamide, dimethyl sulfoxide, and hexamethyl phosphorus. Aprotic polar solvents such as lictriamide or mixed solvents thereof are preferred. In addition, in the above method, when R ⁴ of the compound of formula (D) is a hydrogen atom, after performing the above operation, an inorganic salt and water are further added under neutral conditions and refluxed in a polar solvent. A compound of formula (A) is obtained. The above solvent is preferably a polar solvent such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol dimethyl ether, or dioxane, and the inorganic salt is preferably 1 to 10 equivalents of lithium chloride, sodium chloride, potassium chloride, Lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium chloride, calcium chloride,
Strontium chloride, barium chloride, magnesium bromide, calcium bromide, barium bromide, magnesium iodide, calcium iodide, barium iodide, and the like are preferred. The amount of water added is preferably 5 to 50 equivalents, and the reaction is completed in 1 to 15 hours. Incidentally, the optically active glycidyl ether of formula (B), which is the above-mentioned raw material compound, can be produced by the following method. (In the formula, the symbols R ¹ and * have the same meanings as the symbols R ¹ and * in formula (A).) By reacting the phenol derivative represented by R ¹ OH above with optically active epichlorohydrin in the presence of a base, You can get it by twisting it. Optically active epichlorohydrin is 1 to 10% of the raw material phenol derivative.
An equivalent amount is preferable, and the base used in the reaction is preferably 1 to 5 equivalents based on the raw material phenol derivative. Examples of the base include sodium hydroxide, potassium hydroxide, potassium t-butoxide, and the like. Although the reaction proceeds smoothly without a catalyst, a catalyst such as a quaternary ammonium salt such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, or benzyltrimethylammonium bromide is added to the raw material phenol derivative by 0.01 to 0.1. An equivalent amount can also be added. The reaction can be carried out using optically active epichlorohydrin as a solvent, but if necessary, polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, acetonitrile, t-butyl alcohol, and water can also be used. The reaction is completed at a temperature of 50 to 80°C and a time of 0.5 to 3 hours. In addition, as a method different from the above method, optically active chlorohydrin is produced by reacting a raw material phenol derivative and optically active epichlorohydrin in the presence of an amine of 0.1 to 0.5 equivalent to the phenol derivative as a base, such as morpholine, piperidine, pyridine, etc. There is a method in which glycidyl ether is obtained by ring closure by reacting 1 to 5 equivalents of a base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium t-butoxide, etc. Although this method is a two-step reaction, it has the advantage of easy extraction operation. In this case, the reaction is completed in 3 to 24 hours at 50 to 80°C. Racemic glycidyl ether can be obtained by using racemic epichlorohydrin. As for optically active epichlorohydrin as a raw material, as a high-purity one, the R form is disclosed in Japanese Patent Application Laid-Open No. 1982-132196 and Japanese Patent Application Laid-Open No.
The method described in Publication No. 62-6697, and the S-form are also patent applications.
Those obtained by the method described in No. 62-283393 can be used. Furthermore, the phenol derivative used as a raw material for producing the compound of formula (B) above can be synthesized as follows. However, in Tables 1 to 11 below, R ³ is the formula (A) above.
R ³ ' represents a hydrogen atom or an alkyl group having one ^{fewer carbon atoms than R 3 ,} and X represents a halogen atom. In addition, in Table 6, PH is a phenyl group,
R′ represents a lower alkyl group, and in Table 10, Ts
represents p-toluenesulfonyl group. That is, 4-(4-trans-alkylcyclohexyl)phenol, 4-(4-alkyloxyphenyl)phenol, and 4-(4-alkylphenyl)phenol were prepared by known methods as shown in Tables 1, 2, and 3, respectively. It can be synthesized according to the synthetic route. Also 4-(5-alkyl-2-pyrimidinyl)
phenol, and 4-(5-alkyloxy-
2-pyrimidinyl) phenol is disclosed in Japanese Patent Application Laid-open No. 1983-
According to the method described in Publication No. 189274 and DE-No. 144409, they can be synthesized by the synthetic routes shown in Tables 4 and 5, respectively. Furthermore, 4-[5-(4-alkyloxyphenyl)
-2-pyrimidinyl]phenol and 4-[5
-(4-alkylphenyl)-2-pyrimidinyl]
Phenol can be synthesized according to the synthetic route shown in Table 6. To explain the synthesis method in Table 6, the hydroxyl group of p-hydroxybenzonitrile is protected by benzylation, and the cyano group is converted to amidine hydrochloride using a conventional method.
Synthesize (E). On the other hand, after esterifying p-hydroxyphenylacetic acid with a lower alcohol, the phenolic hydroxyl group is alkylated with an alkylating agent such as an alkyl halide, an alkyl p-toluenesulfonate, or an alkyl methanesulfonate, and then diethyl carbonate is A diethyl malonate derivative (G) is synthesized by reacting with the compound in the presence of a base. After condensing amidine hydrochloride (E) and diethyl malonate derivative (G) using a base such as sodium ethoxide or sodium methoxide, N,
N-diethylaniline, pyridine, 4-N,N-
A dichloropyrimidine derivative is obtained by reacting with phosphorus oxychloride in the presence of a base such as dimethylaminopyridine, and this is reduced with hydrogen gas in the presence of a Pd-C catalyst to produce 4-[5-(4-alkyloxyphenyl). )-2-pyrimidinyl]phenol (I)
Synthesize. Synthesis of (I) using p-alkylphenyl diethyl malonate (F) in place of the diethyl malonate derivative (G) in the synthesis of (I) above, and using (E) and (G) as raw materials According to the reaction process, when (E) and (F) are reacted, 4-[5-(4-alkylphenyl)-2-
[pyrimidinyl]phenol (H) can be synthesized. Diethyl p-alkylphenylmalonate (F) used in this case is synthesized by converting p-alkylacetophenone into a phenylacetic acid derivative by Willgerodt reaction, esterifying it with a lower alcohol, and condensing it with diethyl carbonate. can. In addition, raw material phenol derivatives in which the benzene ring is substituted with a halogen atom or a cyano group are shown in Tables 7 to 11 below.
It can be synthesized by a known method as shown below. The liquid crystal composition of the present invention can be formed by mixing at least one compound of formula (A) obtained by the above method with another chiral liquid crystal, non-chiral liquid crystal, or a mixture thereof. . As chiral liquid crystals other than those mentioned above, all ferroelectric liquid crystals including those conventionally known can be applied, and as non-chiral liquid crystals, liquid crystals that do not have asymmetric carbon atoms and can be smected after mixing. Any material may be used as long as it exhibits C phase. Specific examples of the chiral or non-chiral liquid crystal include compounds represented by the following formula (J). (E, F and G in formula (J) are each independently

【formula】 【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

[Formula] and

It represents a six-membered ring selected from [Formula], and the hydrogen atoms in these six-membered rings are halogen atoms,
It may be substituted with a cyano group or a nitro group.
a and b are 0, 1 or 2, c is 1 or 2, and a+b+c=2-4. W, M are single bonds, or

【formula】 【formula】

【formula】

[Formula] -O-, -S-,

【formula】

[Formula] Represents a group selected from -CH ₂ O- and OCH ₂ -.
When a=0, K represents a single bond, and when b=0, L represents a single bond. When a or b is not 0, K and L are each independently a single bond, or

【formula】

[Formula] −CH ₂ O−, OCH ₂ −, −CH ₂ CH ₂ −, −CH=N−, −N=CH−, −CH
=CH−, −C≡C−,

[Formula] and Beauty

[Formula] represents a group selected from the above formula, R ⁶ and R ⁷ represent a linear or branched alkyl group having 1 to 15 carbon atoms, and these may contain an asymmetric carbon atom) Among the compounds represented by (J), more preferred are compounds represented by the following formula (J-1) or formula (J-2). (In the above formula (J-1), R ⁸ and R ⁹ each represent a linear or branched alkyl group or an alkoxy group having 1 to 15 carbon atoms, and these may contain an asymmetric carbon atom. ) (R ⁸ and R ⁹ in the above formula (J-2) are the above formula (J
-1) has the same meaning as R ⁸ and R ⁹ , and A is

[Formula] or

[Formula] and k and i each independently represent 0 or 1. however,
(k+i = 2) The liquid crystal composition of the present invention is attached with a transparent electrode and sealed in two glass plates whose surfaces have been subjected to surface alignment treatment with polyethylene, polyester, nylon, polyvinyl alcohol, polyimide, etc., and a polarizer is attached to the liquid crystal composition of the present invention. The provided birefringence mode and host-guest mode liquid crystal cell can be used as a display element or an electro-optical element. Note that the racemic form of the compound represented by the general formula (A) used in the present invention can be added to other optically active liquid crystal compounds to adjust the helical pitch thereof. Further, the compound of general formula (A) has good stability against heat and light, and a liquid crystal composition containing this compound has excellent properties as a ferroelectric liquid crystal. moreover,
A liquid crystal composition prepared by adding this compound to a nematic liquid crystal can be used for the following purposes. (1) To suppress the occurrence of reverse domains
Liquid crystal composition added to TN type and STN type liquid crystal. (2) Display element using cholesteric-nematic phase transition effect (JJWysoki, A.Adams and
W. Haas; Phys. Rev. Lett., 20 , 1024 (1968)). (3) Display device using White-Taylor guest-host effect (DLWhite and GN
Taylor; J.Appl.Phys., 45 , 4718 (1974)). (4) Notch filters and bandpass filters (FJKahn; Appl.
Phys. Lett., 18 , 231 (1971)). (5) Circularly polarized beam splitter (SDJacob,
SPIE.37, 98 (1981)). (Example) In each of the following examples, R and S of the optically active compound (A) used in the present invention were expressed based on the position numbers in the chemical formula below. Further, the phase transition temperatures described in the Examples were determined by DSC and polarized light microscopy observation. In addition, the symbols shown in the phase transition temperature section represent the following phases. C; Crystalline phase SmA; Smectic A phase SmC; Smectic C phase SmC ^* ; Chiral smectic C phase Sm1; Unidentified smectic phase other than SmA, SmC, SmC ^* N; Nematic phase N ^* ; Chiral nematic phase I The isotropic liquid phase chiral smectic C phase (SmC ^* ) was further confirmed by measuring the dielectric constant. <Synthesis of phenol derivative> Synthesis example 1 4-[5-(4-n-octyloxyphenyl)
-2-pyrimidinyl]phenol Synthesis of 4-penzyloxyphenylamidine hydrochloride 95.2 g of 4-cyanophenol, 127 g of benzyl chloride, and 138 g of potassium carbonate were dissolved in 160 ml of acetone.
The mixture was refluxed under stirring for an hour. The product was filtered, concentrated under reduced pressure, added with benzene, washed with water, and the benzene was distilled off under reduced pressure to obtain 4-benzyloxybenzonitrile.
Obtained 141.38g. 141g of 4-benzyloxybenzonitrile,
Dissolved in 338 ml of benzene, added 270 ml of ethanol, cooled to 0°C, bubbled hydrogen chloride gas into the resulting slurry solution with stirring, and then lowered the liquid temperature to 25° C.
It was raised to ℃ and left for 2 days. The reaction mixture was concentrated to 1/3 under reduced pressure, ether was added to the concentrated solution,
The precipitated crystals are filtered by suction, and the imide ester is
Obtained 183g. A slurry solution of 183 g of the above imide ester was made with 270 ml of ethanol, a solution of 60.75 g of ammonia gas in 405 ml of ethanol was added thereto, and after being left at room temperature for 2 days, the solvent was distilled off under reduced pressure, and 4-benzyloxyphenylamidine hydrochloride 164.5 I got g. NMR (DMSO-d ₆ ) δ: 5.19 (2H, s) 7.17 (2H, d, J=9.0Hz) 7.35 (5H, s) 7.86 (2H, d) of diethyl 4-n-octyloxyphenylmalonate Synthesis 50.0 g of 4-hydroxyphenylacetic acid was dissolved in 400 ml of ethanol, 0.5 ml of concentrated sulfuric acid was added, the mixture was stirred under reflux, and the ethanol was distilled off to obtain 60 g of ethyl 4-hydroxyphenylacetate. Next, 59 g of ethyl 4-hydroxyphenylacetate,
Dissolve 22.4g of sodium ethoxide in 150ml of ethanol, add 63.5g of n-octyl bromide, and
Stir under reflux for an hour, concentrate the reaction solution under reduced pressure, add ethyl acetate to dissolve the oil, wash with water, dry over anhydrous magnesium sulfate, remove ethyl acetate under reduced pressure, and distill under reduced pressure to give 4-n- 79.6 g of ethyl octyloxyphenyl acetate was obtained. (bp179℃/0.1mmHg) 79g of ethyl 4-n-octyloxyphenyl acetate thus obtained, 140ml of ethanol, 300ml of diethyl carbonate, and 19.3g of sodium ethoxide were mixed,
The mixture was heated and stirred while distilling off the ethanol. After the reaction mixture was transferred to ice water and acidified with hydrochloric acid, the organic layer was separated and the solvent was distilled off to obtain 91.6 g of diethyl 4-n-octyloxyphenylmalonate. NMR (CDCl ₃ ) δ: 0.5 to 2.0 (21H, m) 3.90 (2H, t, J = 6.0Hz) 4.16 (4H, q, J = 7.2Hz) 4.52 (1H, s) 6.80 (2H, d, J =9.0Hz) 7.26 (2H, d, J = 9.0Hz) 4-[5-(4-n-octyloxyphenyl)
Synthesis of -2-pyrimidinyl]phenol 4-benzyloxyphenylamidine hydrochloride
65.6 g and 91.0 g of diethyl 4-n-octyloxyphenylmalonate were dissolved in 500 ml of methanol, 44.8 g of sodium methoxide was added, and the mixture was stirred under reflux for 9 hours. After cooling, the reaction mixture was made acidic with sulfuric acid, and the precipitated crystals were collected by suction filtration to obtain 77.7 g of yellow crystals. 77g of the above yellow crystals and 310ml of phosphorus oxychloride, N,
46.5 ml of N-diethylaniline was stirred under reflux for 26 hours. After removing excess phosphorus oxychloride under reduced pressure, the residue was transferred to ice water, extracted with ether, washed with water, and the ether was distilled off to obtain 70 g of a crude product. This was recrystallized from ether to obtain 21 g of a compound represented by the following chemical formula. (Ph is a phenyl group) NMR (CDCl ₃ ) δ: 0.4-2.1 (15H, m) 3.99 (2H, t, J = 6.0Hz) 5.09 (2H, s) 6.7-7.5 (11H, m) 8.38 (2H, d, J = 9.0 Hz) 19.8 g of the above colorless crystals, 757 ml of ethanol, 11.4 g of magnesium oxide, 57 ml of water, and 4 g of 10% Pd-C were heated and stirred at 60° C. under a hydrogen atmosphere until the theoretical amount of hydrogen was absorbed. The reaction mixture was filtered under suction, and 7.7 g of 4-[5-(4-n-octyloxyphenyl)-2-pyrimidinyl]phenol represented by the following chemical formula was obtained from the filtrate. mp 137℃ NMR (CDCl ₃ ) δ: 0.5 to 2.1 (15H, m) 4.00 (2H, t, J = 6.0Hz) 6.92 (2H, d, J = 9.0Hz) 7.01 (2H, d, J = 9.0Hz ) 7.50 (2H, d, J=9.0Hz) 8.31 (2H, d, J=9.0Hz) 8.94 (2H, s) Synthesis example 2 4-(4-n-octylphenyl)phenol
2.82 g of boron trichloride and 40 ml of 1,2-dichloroethane were added with 2M boron trichloride under ice cooling.
6 ml of dichloroethane solution was added, followed by 0.82 ml of methyl thiocyanate and 1.33 g of aluminum chloride. The mixture was stirred at room temperature until the aluminum chloride was dissolved, and then stirred at 80°C for 3 hours. After cooling, add 33ml of 4N sodium hydroxide aqueous solution to 75~
Stirred at 80°C for 30 minutes. After cooling, the reaction solution was washed with methylene chloride, and the aqueous layer was adjusted to pH=2 with 6N hydrochloric acid.
Extracted with ether. After drying the extract, the ether was distilled off under reduced pressure, and the resulting crude crystals were purified by silica gel column chromatography to obtain 4-(4-n-octylphenyl)-2-, which is represented by the chemical formula below.
2.03g of cyanophenol was obtained. mp 93℃ NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.8Hz) 1.27 - 1.32 (10H, m) 1.60 - 1.71 (2H, m) 2.64 (2H, t, J = 7.7Hz) 6.24 ( 1H, broad S) 7.02-7.70 (7H, m) IR (KBr) 3288cm ^-1 (νO-H) 2240cm ^-1 (νC≡N) <Synthesis of compound of formula (B)> As the raw material optically active epichlorohydrin, this application JP-A-61-132196, JP-A-62-
6697 and the method described in Japanese Patent Application No. 62-283393 were used. These substances are R-(-) and S-(+)-epichlorohydrin, and as determined by gas chromatographic analysis, their chemical purity is 98.5% or higher, and their optical purity is 99% or higher (specific optical rotation is [α]) ²⁵ _D =
34.0°, +34.0°; C=1.2, methanol). Synthesis Example 3 4.25g of the above R-(-)-epichlorohydrin,
2.50g of a phenol derivative represented by the chemical formula below, and benzyltriethylammonium chloride 20
Dissolve mg in 3 ml of dimethylformamide and 60°C.
24 wt% aqueous sodium hydroxide solution (1.2 equivalents)
was dripped. After reacting at the same temperature for 40 minutes, the reaction solution was returned to room temperature, then extracted with ether, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.62 g of S-glycidyl ether represented by the following chemical formula. mp 90℃ [α] ²⁵ _D +4.44° (C=1.01, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.50 to 3.00 (19H, m) 3.10 to 3.50 (1H, m) 3.80 to 4.30 (2H , m) 6.75-7.60 (8H, m) Synthesis Example 4 13 g of a compound represented by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin as in Synthesis Example 3
13.2 g of potassium t-butoxide, 8.8 g of potassium t-butoxide, and 80 ml of t-butyl alcohol were mixed and stirred at 60°C for 2 hours. After concentrating the mixture, chloroform was added, washed with saturated brine, and dried over anhydrous magnesium sulfate. The crude product obtained by distilling off chloroform under reduced pressure was purified by silica gel column chromatography to obtain 14.2 g of S-glycidyl ether represented by the following chemical formula. mp 90℃ [α] ³⁰ _D +4.78° (C=1.082, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 to 3.0 (15H, m) 3.10 to 3.50 (1H, m) 3.80 to 4.40 (2H , m) 6.85-7.60 (8H, m) Synthesis Example 5 Compound represented by the following chemical formula as a raw material phenol derivative An R-glycidyl ether represented by the following chemical formula was obtained in the same manner as in Synthesis Example 4, except that the above S-(+)-epichlorohydrin was used instead of R-(-)-epichlorohydrin. mp 91℃ [α] ³⁵ _D −3.59° (C=1.07, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.85 to 2.93 (27H, m) 3.34 to 3.40 (1H, m) 3.97 to 4.27 (2H, m) 6.94-7.53 (8H, m) Synthesis Example 6 10.0g of a compound represented by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin as in Synthesis Example 3
18.6g, piperidine 367mg and dimethylformamide 1ml were mixed and stirred at 60°C for 10 hours. The solvent was distilled off from the reaction solution under reduced pressure, 5 ml of acetone was added, and a 24% by weight aqueous sodium hydroxide solution (1.2 equivalents) was added dropwise with stirring at room temperature, followed by reaction for 30 minutes. After adjusting the pH to 7 by adding 2N hydrochloric acid, the mixture was extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.58 g of S-glycidyl ether represented by the following chemical formula. mp 131℃ [α] ²⁷ _D +3.03° (C=0.55, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.70-2.20 (17H, m) 2.55-3.00 (2H, m) 3.15-3.45 (1H , m) 3.75-4.20 (2H, m) 6.89 (2H, d, J = 9.0Hz) 6.92 (2H, d, J = 8.4Hz) 7.43 (4H, d, J = 9.0Hz) Synthesis example 7 Raw material phenol derivative 10g of the compound represented by the chemical formula below, R-(-)-epichlorohydrin as in Synthesis Example 3
16.07g, 20% by weight sodium hydroxide aqueous solution 7.33g
and dimethylformamide 20ml mixture 60-70
The mixture was heated and stirred at ℃ for 1 hour. After cooling the reaction solution, water was added and the product was extracted with dichloromethane to obtain 11.67 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 9.07 g of S-glycidyl ether represented by the following chemical formula. mp 74℃ [α] ²⁴ _D +1.66° (C=1.02, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.5 to 2.2 (15H, m) 2.6 to 3.0 (2H, m) 3.1 to 3.7 (1H , m) 3.8-4.4 (4H, m) 6.95 (2H, d, J = 9.0Hz) 8.26 (2H, d, J = 9.0Hz) 8.36 (2H, s) Synthesis example 8 Synthesis example 1 as the raw material phenol derivative 7.44g of the obtained compound represented by the following chemical formula, R-(-)-epichlorohydrin as in Synthesis Example 3
A mixture of 9.16 g, 1.74 g of 50% by weight aqueous sodium hydroxide solution and 77 ml of dimethylformamide was heated at 60 to 70°C.
The mixture was stirred for 3 hours. After cooling the reaction solution, water was added, the product was extracted with dichloromethane, and the extract was purified by silica gel column chromatography to obtain 6.90 g of S-glycidyl ether represented by the chemical formula below.
I got it. mp 198℃ [α] ²⁵ _D +0.95° (C=1.04, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.6 to 2.1 (15H, m) 2.6 to 3.0 (2H, m) 3.2 to 3.5 (1H , m) 3.8~4.5 (2H, m) 6.99 (4H, d, J=9.0Hz) 7.50 (2H, d, J=9.0Hz) 8.40 (2H, d, J=9.0Hz) 8.90 (2H, s) Synthesis Example 9 1.01g of a compound represented by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin as in Synthesis Example 3
2.01 g and 16 mg of benzyltriethylammonium chloride were mixed and heated to 70°C, and 650 mg of a 24% by weight aqueous sodium hydroxide solution was added dropwise thereto. 70
After stirring at °C for 2 hours, the reaction solution was allowed to reach room temperature, then extracted three times with chloroform and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was recrystallized from hexane to obtain 380 mg of S-form glycidyl ether represented by the following chemical formula. mp 65℃ [α] ²⁵ _D +1.90° (C=0.46, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.6 to 3.0 (19H, m) 3.2 to 3.6 (1H, m) 3.9 to 4.5 (2H , m) 6.99 (2H, d, J = 9.0Hz) 8.36 (2H, d, J = 9.0Hz) 8.55 (2H, s) Synthesis example 10 3.12g of the compound shown by the chemical formula below as a raw material phenol derivative, 4.627 g of R-(-)-epichlorohydrin as in Synthesis Example 3, 50% by weight aqueous sodium hydroxide solution
A mixture of 0.88g and 30ml dimethylformamide
The mixture was heated and stirred at 60°C for 2.5 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure, and the product was purified by silica gel column chromatography to obtain 2.96 g of S-glycidyl ether represented by the following chemical formula. mp 65℃ [α] ²⁷ _D +2.47° (C=1.02, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.6 to 2.0 (19H, m) 2.4 to 3.0 (4H, m) 3.2 to 3.5 (1H , m) 3.8-4.5 (2H, m) 6.98 (2H, d, J = 9.0Hz) 8.33 (2H, d, J = 9.0Hz) 8.53 (2H, s) Synthesis example 11 4 obtained in synthesis example 2 -(4-n-octylphenyl)-2-cyanophenol 1.9 g and t-
832 mg of potassium t-butoxide was added to a solution consisting of 40 ml of butyl alcohol, and then 2.5 ml of the same R-(-)-epichlorohydrin as in Synthesis Example 3 and 100 mg of 4-(N,N-dimethylamino)pyridine were added. Stirred at room temperature for 2 days. The mixture was concentrated under reduced pressure, water was added to the residue, extracted with ether, and the extract was dried. The crude product obtained by distilling off the ether from the extract was purified by silica gel column chromatography to obtain 750 mg of S-glycidyl ether represented by the following chemical formula. mp 54℃ [α] ²³ _D +7.88° (C = 1.01, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 (3H, t, J = 6.6Hz) 1.20 ~ 1.42 (10H, m) 1.55 ~ 1.67 (2H, m) 2.64 (2H, t, J=7.7Hz) 2.84~2.97 (2H, m) 3.39~3.43 (1H, m) 4.12~4.45 (2H, m) 7.05~7.77 (7H, m) IR (KBr) 2224cm ^-1 (νc≡N) <Synthesis of formula A compound> Example 1 S-form glycidyl ether obtained in Synthesis Example 3
370 mg of diethyl n-propylmalonate, 442 mg of diethyl n-propylmalonate, 134 mg of potassium t-butoxide, and 3 ml of t-butyl alcohol were mixed and stirred under reflux for 10 hours. After returning the reaction solution to room temperature and adding 4N hydrochloric acid to adjust the pH to 1,
White crystals were obtained by washing with water and methanol. This was separated and purified by silica gel chromatography to obtain a γ-lactone derivative (2S,
240 mg of the 4S) body and 140 mg of the (2R,4S) body were obtained. (2S, 4S) body Phase transition temperature C115℃ ---→ I [α] ²⁶ _D +32.67° (C=1.081, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.70 to 3.00 (27H, m) 4.00 to 4.25 (2H, m) 4.40~4.85 (1H, m) 6.60~7.60 (8H, m) IR (KBr) 1762cm ^-1 (2R, 4S) body Phase transition temperature C117℃ ---→ I [α] ²⁶ _D +22.50° (C=0.504, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.70 to 3.00 (27H, m) 4.00 to 4.25 (2H, m) 4.50-5.00 (1H, m) 6.60-7.60 (8H, m) IR (KBr) 1762cm ^-1 Example 2 S-form glycidyl ether obtained in Synthesis Example 4
365 mg of dimethyl malonate, 232 mg of dimethyl malonate, 138 mg of potassium t-butoxide and 2 ml of t-butyl alcohol were mixed and stirred under reflux for 2 hours. After cooling the reaction solution to room temperature, 4N hydrochloric acid was added to adjust the pH to 1, followed by extraction with chloroform three times, washing with saturated brine, and drying over anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was purified by silica gel chromatography to obtain a (4S) 2-(methoxycarbonyl)γ-lactone derivative represented by the following formula:
Obtained 226 mg. IR (KBr) 1740, 1768 cm ^-1 followed by 200 mg of the above compound, magnesium chloride
232mg, dimethylacetamide 1.5ml and water 0.5ml
The mixture was mixed and stirred under reflux for 10 hours. After the reaction solution was returned to room temperature, it was extracted twice with chloroform, washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 145 mg of a (4S)-form γ-lactone derivative represented by the following formula. Phase transition temperature C138℃ ---→ I [α] ³⁰ _D +19.16° (C=1.03, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.80 to 1.75 (11H, m) 2.15 to 2.85 (6H, m) 4.05-4.30 (2H, m) 4.75-4.95 (1H, m) 6.85-7.60 (8H, m) IR (KBr) 1764 cm ^-1 Example 3 R obtained in Synthesis Example 5 as optically active glycidyl ether Using the body glycidyl ether, n-
The (2R, 4R) and (2S, 4R) forms of a γ-lactone derivative were obtained in the same manner as in Example 1, except that n-butyl dimethyl malonate was used instead of diethyl propyl malonate. (2R,4R) body Phase transition temperature C130℃ ---→ I [α] ³⁴ _D −28.56° (C=1.06, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.85 to 2.69 (37H, m) 4.15 to 4.18 (2H, m ) 4.71~4.77 (1H, m) 6.95~7.53 (8H, m) IR (KBr) 1764cm ^-1 (2S, 4R) body Phase transition temperature C128℃ ---→ I [α] ³⁴ _D −22.98° (C=1.07, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.85 to 2.85 (37H, m) 4.08 to 4.21 (2H, m ) 4.81-4.86 (1H, m) 6.93-7.52 (8H, m) IR (KBr) 1760cm ^-1 Example 4 S-form glycidyl ether obtained in Synthesis Example 6
260 mg of dimethyl n-heptylmalonate, 90 mg of potassium t-butoxide and 2 ml of t-butyl alcohol were mixed and stirred under reflux for 13 hours. The treatment after the reaction was carried out in the same manner as in Example 1 to obtain white crystals.
This was separated and purified by silica gel chromatography to obtain 43 mg of the (2S,4S) form of the γ-lactone derivative represented by the following formula. Phase transition temperature C139℃ ---→ I [α] ³⁰ _D +28.59° (C=0.674, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.70 to 2.95 (37H, m) 3.80 to 4.20 (4H, m) 4.45 to 4.90 (1H, m) 6.90 (4H, d, J = 9.0Hz) 7.42 (4H, d, J = 9.0Hz) IR (KBr) 1760cm ^-1 Example 5 S obtained in Synthesis Example 8 body glycidyl ether
Dissolve 518 mg, dimethyl n-pentylmalonate, 970 mg, and potassium t-butoxide 269 mg in 5 ml of dimethylformamide and 5 ml of t-butyl alcohol.
The mixture was heated and stirred at 90°C for 5 hours. The treatment after the reaction was carried out in the same manner as in Example 1 to obtain a γ-lactone derivative represented by the following formula. This compound is a mixture of diastereomers, and the (2R,4S) form was further isolated by silica gel chromatography. (2R,4S) body Phase transition temperature C138℃ ―――→ ←――― 134℃Sm1145℃ ――――→ ←――― 145℃SmC ^* 201℃ ――――→ ←――― 201℃N ^* 202℃ ――――→ ← --- 202℃I NMR (CDCl ₃ ) δ: 0.4 ~ 3.0 (29H, m) 3.7 ~ 4.3 (4H, m) 4.82 (1H, m) 7.00 (4H, d, J = 9.0Hz) 7.50 (2H, d, J = 9.0Hz) 8.39 (2H, d, J = 9.0Hz) 8.85 (2H, s) IR (Nudiyol) 1778cm ^-1 Example 6 S-form glycidyl ether obtained in Synthesis Example 9
320mg of dimethyl n-hexylmalonate, 406mg of dimethyl n-hexylmalonate, and 116mg of potassium t-butoxide were dissolved in 3.5ml of t-butyl alcohol and stirred under reflux for 6 hours. The post-reaction treatment was carried out in the same manner as in Example 1, and a mixture of diastereomers of γ-lactone derivatives ((2S,4S)/
(2R,4S)=9/1) 270 mg was obtained. (2S, 4S) body (2R,4S) body Physical properties of mixture Phase transition temperature C116℃ ---→ I [α] ²⁵ _D +37.93° (C=1.024, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.50 to 2.80 (33H, m) 4.10 to 4.25 (2H, m) 4.45 to 4.85 (1H, m) 6.95 (2H, d, J = 9.0Hz) 8.34 (2H, d, J = 9.0Hz) 8.52 (2H, s) IR (nujior) 1778cm ^-1 Example 7 Using the S-form glycidyl ether obtained in Synthesis Example 10 as an optically active glycidyl ether, n-
The (2S,4S) and (2R,4S) forms of γ-lactone derivatives were obtained in the same manner as in Example 6, except that dimethyl n-dodecylmalonate was used instead of dimethyl hexylmalonate. (2S, 4S) body Phase transition temperature C127℃ ---→ I [α] ³¹ _D +26.01° (C=1.062, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.5 to 2.9 (49H, m) 4.19 (2H, m) 4.82 (1H, m) 6.95 (2H, d, J = 9.0Hz) 8.32 (2H, d, J = 9.0Hz) 8.52 (2H, s) IR (nujiol) 1778cm ^-1 (2R, 4S) body Phase transition temperature C89℃ ---→ I [α] ³¹ _D +17.12° (C=0.398, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.5 to 2.9 (49H, m) 4.19 (2H, m) 4.81 (1H, m) 6.95 (2H, d, J = 9.0Hz) 8.32 (2H, d, J = 9.0Hz) 8.52 (2H, s) IR (Nujiol) 1778cm ^-1 Example 8 Obtained in Synthesis Example 8 S-glycidyl ether
518mg, dimethyl n-undecylmalonate 1.37g,
269 mg of potassium t-butoxide was dissolved in 5 ml of dimethylformamide and 5 ml of t-butyl alcohol, and the mixture was heated and stirred at 90°C for 3 hours. The treatment after the reaction was carried out in the same manner as in Example 1 to obtain 733 mg of a γ-lactone derivative represented by the following formula. This is a mixture of diastereomers, and by silica gel chromatography, the (2S, 4S) and (2R,
4S) The body was fractionated. (2S, 4S) body Phase transition temperature C150℃ ―――→ ←――― 147℃Sm1155℃ ――――→ ←――― 155℃SmC ^* 183℃ ――――→ ←――― 180℃I [α] ³¹ _D +20.93 ° (C = 1.116, CHCl ₃ ) NMR (CDCl ₃ ) δ: 0.4 ~ 3.0 (41H, m) 3.7 ~ 4.3 (4H, m) 4.71 (1H, m) 7.00 (4H, d, J = 9.0Hz) 7.50 (2H, d, J = 9.0Hz) 8.39 (2H, d, J = 9.0Hz) 8.89 (2H, s) IR (nujiol) 1778cm ^-1 (2R, 4S) body Phase transition temperature C120℃ ―――→ ←――― 114℃Sm1133℃ ――――→ ←――― 131℃SmC ^* 195℃ ――――→ ←――― 192℃I NMR (CDCl ₃ ) δ: 0.4 ~3.0 (41H, m) 3.7~4.3 (4H, m) 4.83 (1H, m) 7.00 (4H, d, J = 9.0Hz) 7.50 (2H, d, J = 9.0Hz) 8.39 (2H, d, J =9.0Hz) 8.89 (2H, s) IR (Nudiyol) 1778cm ^-1 Example 9 S-form glycidyl ether obtained in Synthesis Example 7
1.00g, dimethyl methylmalonate 677mg, potassium t-butoxide 630mg and dimethylformamide 10
ml and 10 ml of t-butyl alcohol, and the mixture was heated and stirred at 90°C for 2 hours. The treatment after the reaction was carried out in the same manner as in Example 1 to obtain 810 mg of a γ-lactone derivative represented by the following formula. This product was a mixture of diastereomers, and the (2S,4S) and (2R,4S) forms were separated by silica gel chromatography. (2S, 4S) body Phase transition temperature C154℃ ---→ I NMR (CDCl ₃ ) δ: 0.5 to 3.0 (21H, m) 3.9 to 4.3 (4H, m) 4.65 (1H, m) 6.93 (2H, d, J = 9.0Hz) 8.25 (2H, d, J=9.0Hz) 8.37 (2H, s) IR (nujiol) 1780cm ^-1 (2R, 4S) body Phase transition temperature C115℃ ---→ I NMR (CDCl ₃ ) δ: 0.5 ~ 3.0 (21H, m) 3.9 ~ 4.3 (4H, m) 4.75 (1H, m) 6.93 (2H, d, J = 9.0Hz) 8.25 (2H, d, J = 9.0Hz) 8.37 (2H, s) IR (Nudiyol) 1780cm ^-1 Example 10 S-form glycidyl ether obtained in Synthesis Example 11
363 mg of diethyl n-propylmalonate, 157 mg of potassium t-butoxide and 10 ml of t-butyl alcohol were mixed and stirred under reflux for 6 hours. The reaction solution was returned to room temperature, water was added, the pH was adjusted to 2 with 4N hydrochloric acid, and the mixture was extracted with chloroform. The oil obtained from the extract was separated and purified by silica gel chromatography to obtain 33 mg of the (2S,4S) form and 25 mg of the (2R,4S) form of γ-lactone derivatives represented by the following formulas. (2S, 4S) body Phase transition temperature C86℃ ---→ I [α] ²³ _D +31.83° (C=1.09, CH ₂ Cl ₂ ) NMR (CHCl ₃ ) δ: 0.88 (3H, t, J=6.6Hz) 0.97 (3H , t, J=7.1Hz) 1.25-1.32 (10H, m) 1.41-1.58 (3H, m) 1.59-1.66 (2H, m) 1.85-2.07 (2H, m) 2.55-2.78 (4H, m) 4.31 ( 2H, d, J=4.3Hz) 4.74~4.83 (1H, m) 7.00~7.77 (7H, m) IR (KBr) 2232cm ^-1 (νC≡N) 1768cm ^-1 (νC=O) (2R, 4S) body Phase transition temperature C80℃ ---→ I [α] ²³ _D +18.26° (C=0.87, CH ₂ Cl ₂ ) NMR (CDCl ₃ ) δ: 0.88 ( 3H, t, J=6.8Hz) 0.98 ( 3H , t, J=7.1Hz) 1.25-1.27 (12H, m) 1.45-1.56 (2H, m) 1.60-1.62 (1H, m) 1.85-1.95 (1H, m) 2.12-2.22 (1H, m) 2.56- 2.67 (3H, m) 3.05~3.10 (1H, m) 4.19 (1H, dd, J=3.3Hz, 10.3Hz) 4.37 (1H, dd, J=3.3Hz, 10.3Hz) 4.84~4.89 (1H, m) 7.00 to 7.77 (7H, m) IR (KBr) 2232cm ^-1 (νC≡N) 1768cm ^-1 (νC=O) <Physical properties of liquid crystal composition containing compound of formula A> Example 11 Obtained in Example 1 (2S,4S) form of γ-lactone derivative represented by the following formula and a compound represented by the following chemical formula (1) The composition is a mixture of the following at a ratio of 1:15.6 (by weight):
70Hz, using DSC measurement, polarization microscope observation, and a 22μm thick cell made of Nesa glass.
The phase transition temperature (℃) is C31℃ ---→ ← --- 27℃SmC ^* 61℃ ---→ ← --- 55℃SmA65℃ ―――→ ←――― 63℃N ^* 68℃ ―――→ ←―――― It was found that 67℃I. The measurement results of the dielectric constant of the composition are shown in FIG. It has been found that the above-mentioned γ-lactone derivative ((2S,4S) derivative) does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds. Example 12 (2R,4S) form of the γ-lactone derivative represented by the following formula obtained in Example 1 and the compound of formula (1) used in Example 11 at a ratio of 1:18.0
The phase transition temperature of the composition mixed in the ratio of (weight) is
As a result of measurement in the same manner as in Example 11, C31℃ ―――→ ←――― 26℃SmC ^* 63℃ ――――→ ←――― 53℃SmA64℃ ――――→ ←――― 63℃N ^* 68℃ ――→ ←―――― It was confirmed that it was 66℃I. The measurement results of the dielectric constant of the composition are shown in FIG. It has been found that the above γ-lactone derivative ((2R,4S) derivative) does not exhibit ferroelectricity by itself, but exhibits ferroelectricity when mixed with other liquid crystal compounds. Example 13 (4S) form of the γ-lactone derivative represented by the following formula obtained in Example 2 and a compound represented by the following chemical formula (2) A liquid crystal composition was obtained by mixing these in a ratio of 1:19 (by weight). As a result of measuring the response speed of this composition, it was found that this composition exhibited a high-speed response of 490 μsec (40° C.). The response speed was determined from the change in transmitted light intensity when the above composition was sealed in a 2 μm thick cell treated with an alignment agent and a voltage of V _pp =20 V under crossed Nicols was applied. As a spacer
PET film, polyimide film as alignment agent,
Furthermore, an ITO electrode was used as the electrode, and the rubbing direction was parallel. Example 14 (2R,4R) form of the γ-lactone derivative obtained in Example 3 and represented by the following formula and the compound of formula (2) used in Example 13 were mixed at a ratio of 1:19 (by weight) to obtain a liquid crystal composition. The response speed of this composition was measured in the same manner as in Example 13, and it was found that this composition exhibited a high-speed response of 75 μsec (40° C.). Example 15 (2S,4S) form of the γ-lactone derivative represented by the following formula obtained in Example 4 and the compound of formula (1) used in Example 11 at a ratio of 1:15.9
The phase transition temperature of the composition mixed at the ratio of (weight) was determined in the same manner as in Example 11, and the results were as follows: C31℃ ---→ ←---- 25℃SmC ^* 58℃ ---→ ←---- 58 ℃SmA66℃ ―――→ ←――― 63℃N ^* 71℃ ―――→ ←――― 68℃I was confirmed. The measurement results of the dielectric constant of the composition are shown in FIG. It has been found that the above-mentioned γ-lactone derivative does not exhibit ferroelectricity when used alone, but exhibits ferroelectricity when mixed with other liquid crystal compounds. Example 16, Comparative Example 1 (2S,4S) form of the γ-lactone derivative represented by the following formula obtained in Example 4 and a smectic liquid crystal composition in the proportions shown in Table 12 to obtain a liquid crystal composition. The response speed of this composition was measured by the same method as in Example 13, and it was found that the response speed was greatly improved compared to Comparative Example 1 in which no γ-lactone derivative was blended.

[Table] Example 17 (2R,4S) form of the γ-lactone derivative represented by the following formula obtained in Example 5 and the compound of formula (1) used in Example 11 at a ratio of 1:8.4 (by weight), the phase transition temperature of the composition was measured in the same manner as in Example 11, and was found to be C31℃ --- → ←――― 27℃SmC ^＊ 70℃ ―――→ ←――― 60℃SmA72℃ ――――→ ←――― 71℃N ^＊ 77℃ ―――→ ←――― 77℃I It turned out that. The phase transition temperature of the compound of formula (1) above is C24℃ ←――→ SmC ^* 58℃ ←――→ SmA64℃ ←――→ N67℃ ←――→ I, and it does not exhibit ferroelectricity. It was found that ferroelectricity was developed by mixing it with other liquid crystal compounds, and that the temperature range in which ferroelectricity was exhibited was significantly expanded compared to the temperature range of the original SmC phase. Similar measurements were also performed on the (2S, 4S) form, which was collected together with the (2R, 4S) form of the γ-lactone derivative, and the same effects as the (2R, 4S) form were observed. Example 18 A mixture of diastereomers of the γ-lactone derivative represented by the following formula obtained in Example 6 ((2S,
4S) / (2R, 4S) = 9/1) (2S, 4S) body (2R,4S) body and the compound of formula (1) used in Example 11 in a ratio of 1:9.7 (by weight), the phase transition temperature of the composition was measured in the same manner as in Example 11, and was found to be C24°C ←―― → SmC ^* 24℃ ←――→ SmA24℃ ←――→ N ^* 24℃ ←――→ I. The measurement results of the dielectric constant of the composition are shown in FIG. (2S,4S) form of the above γ-lactone derivative,
It was found that (2R,4S) mixtures do not exhibit ferroelectricity when used alone, but when mixed with other liquid crystal compounds, a ferroelectric phase appears. Example 19 (2S,4S) form of the γ-lactone derivative represented by the following formula obtained in Example 7 and the compound of formula (2) used in Example 13 were mixed at a ratio of 1:19 (by weight) to obtain a liquid crystal composition. The response speed of this composition was measured in the same manner as in Example 13, and it was found that this composition exhibited a high-speed response of 300 μsec (40° C.). Examples 20 to 21 γ-lactone derivative ((2S,4S) derivative) obtained in Example 8 and represented by the following formula and the γ-lactone derivative (2S, 4S) obtained in Example 9 and represented by the following formula: (2R,4S) body The liquid crystal compounds shown in Table 13 were prepared using a 1:1 mixture of the (2S,4S) and (2R,4S) forms of It was measured by the method. The response speed when the γ-lactone derivative was not mixed was 1800 μsec (50°C) as shown in Comparative Example 1, but as is clear from Table 13, the response speed was 1800 μsec (50°C) when the γ-lactone derivative of the present invention was not mixed. The composition showed a faster response and was found to be very effective for use in display devices or optical devices.

【table】

[Table] Example 22 The (2S,4S) form of the optically active γ-lactone derivative obtained in Example 10 and the following chemical formula (3), It was found from DSC measurement and observation using a polarizing microscope that the phase transition temperature of a composition prepared by mixing the compound represented by the following at a ratio of 1:19 (by weight) is as follows. C30℃ ――――→ ←――― 22℃SmC ^* 57℃ ―――→ ←――― 56℃SmA72℃ ――――→ ←――― 71℃I The above optically active γ-lactone derivative (2S, 4S)
It was found that although the liquid crystal compound alone does not exhibit ferroelectricity, it exhibits ferroelectricity when mixed with other liquid crystal compounds. Further, the response speed of the above composition measured in the same manner as in Example 13 was found to exhibit a high-speed response of 128 μsec (40° C.). Example 23 (2R,4S) form of the optically active γ-lactone derivative obtained in Example 10 and the formula used in Example 22
The phase transition temperature of a composition prepared by mixing compound (3) at a ratio of 1:19 (weight) was measured in the same manner as in Example 22, and the results were as follows. C30.7℃ ---→ ←---- 22℃SmC ^* 55.3℃ ---→ ←――- 53.8℃SmA71.2℃ ---→ ←――- 70.4℃I The above optically active γ-lactone derivative (2R, 4S)
It was found that although the liquid crystal compound does not exhibit ferroelectricity by itself, it exhibits ferroelectricity when mixed with other liquid crystal compounds. Further, as a result of measuring the response time of the above composition in the same manner as in Example 13, it was found that it exhibited a high-speed response of 98 μsec (40° C.). (Effect of the invention) The novel liquid crystal composition according to the present invention has an optically active γ-
It is characterized by containing a lactone-based liquid crystal compound,
Since the optically active γ-lactone liquid crystal compound has large spontaneous polarization and chemical stability, it provides a chemically stable liquid crystal composition with a significantly faster response speed than conventional liquid crystal compositions.

[Brief explanation of drawings]

Figures 1 to 4 show Examples 11, 12, and 15, respectively.
and 18 are graphs showing the relationship between temperature and relative permittivity of liquid crystal compositions.

Claims (1)

[Claims] 1 General formula (A) (R ¹ in formula (A) is [formula] or , n or e is each independently 0 or 1,
^R3 is an alkyl group having 1 to 15 carbon atoms, X or Y is an atom or group selected from a hydrogen atom, a halogen atom, and a cyano group, ^R2 is (-CO-) ^mR4 , and m is 0 or 1 , R ⁴ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and the symbol * represents an asymmetric carbon atom). Characteristic liquid crystal composition. 2 Claim 1 wherein the compound of general formula (A) is a racemate
The liquid crystal composition described. 3. An electro-optical element using the liquid crystal composition according to claim 1 or 2.