JPH02138274A - Liquid crystal compound and its production - Google Patents

Abstract

NEW MATERIAL:A liquid crystal compound bearing an optically active gamma-lactone ring [R<1> is formulas II, III, or IV (n, e are 0, 1; R<3> is 1-15C alkyl); R<2> is -(CO)mR<4> (R<4> is 1-15C alkyl), * means asymmetric carbon atom). EXAMPLE:The compound of formula V. USE:A liquid crystal compound for display elements or electrooptical elements. The asymmetric part is directly connected to the 5-membered ring to restrict the free rotation so that the compound is chemically stabilized with stabilized ferroelectricity. PREPARATION:The reaction of an optically active glycidyl ether of formula VI with a beta-ketoester derivative of formula VII or and a malonic acid ester of formula VIII (R<5> is lower alkyl) is conducted in an organic solvent in the presence of an base to give a liquid crystal compound having an optically active gamma-lactone ring of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel liquid crystal compound used in display elements or electro-optical elements, and a method for producing the same. The liquid crystalline compounds referred to in the present invention include not only substances whose liquid crystal state can be observed by themselves, but also compounds that are useful as constituents of liquid crystal compositions even if they themselves do not exhibit a liquid crystal phase.

(Prior art and its problems) Liquid crystals have come to be widely used as display materials, but currently only TN (Dingwtste) is the display method.
dNematic) type is generally adopted.

This TN display method has advantages such as low power consumption and light-receiving type that does not cause eye fatigue, but since the drive is basically based on the anisotropy of dielectric constant, its power is weak and the response speed is low. It has the disadvantage of being slow, which limits its application to fields that require high-speed response.

Ferroelectric liquid crystal was developed in 1975 by R, B, )feyer
It was first discovered by et al. (J, ph
ystque.

36, L-69 (1975)), this device has an extremely fast response speed as the driving force is a relatively large force derived from spontaneous polarization, and has excellent performance in that it has memory properties, making it a new display element. It is attracting attention as As a condition for liquid crystal to exhibit ferroelectricity, it is necessary to exhibit chiral smectic C phase (SmC" phase), and for this reason, the molecule must contain asymmetric carbon. Also, it must have a chiral smectic C phase (SmC" phase). It is necessary to have a dipole moment in the vertical direction.

) Ferroelectric liquid crystal DOBAHBC synthesized by 1eyeer et al.
Although it satisfies the above conditions, it is chemically unstable because it contains a Schiff base, and its spontaneous polarization is 3×10→C/c.
It was as small as tA. Since then, many ferroelectric liquid crystal compounds have been synthesized, but no one with sufficiently high response speed has yet been found, and therefore has not been put into practical use.

Comparing these conventional ferroelectric liquid crystal compounds, for example, DOBA-1-MBC, in which the asymmetric carbon atom of DOBAMBC is one position closer to the carbonyl group, has a spontaneous polarization of 5xlO''''8C/ci, and DOBA-1-MBC has a spontaneous polarization of 5xlO''''8C/ci; ) is larger than IBc. This is thought to be due to the fact that the asymmetric carbon, which is an important element for the appearance of ferroelectricity, and the dipole are closer together, which suppresses the free rotation of the dipole part of the molecule and improves the orientation of the dipole. It will be done. 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. I can't do it,
It is thought that satisfactory spontaneous polarization and fast response could not be obtained because the dipole part could not be fixed.

(Means for Solving the Problems) The present invention provides a structure in which an asymmetric moiety is directly connected to a 5-membered ring lactone as a means for suppressing the free rotation of the dipole portion of a conventional ferroelectric liquid crystal compound. The object of the present invention is to provide a novel liquid crystal compound that has ferroelectricity that is bound and chemically stable.

The novel compound according to the present invention has the general formula (A>(formula (A>in which R
1 is a selected group, n or e is each independently O or 1
, R3 is an alkyl group having 1 to 15 carbon atoms, R2 is +Go-
)-FR4, m is 0 or 1, R4 represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and the symbol * represents an asymmetric carbon atom) Liquid crystalline material having an optically active γ-lactone ring It is a compound. Examples of the alkyl groups for R3 and R4 here 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-methylhebutyl, 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, 1-methylnonyl.

Examples include groups such as 3.7-dimethyloctyl and 3,7.11-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 carbonyl groups on the ring.
By having two asymmetric carbons, 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 achieving high-speed response. It is something. In addition, in the liquid crystal compound of the present invention (A>, when R2 is a hydrogen atom, there is one type, but compounds where R2 is other than a hydrogen atom contain two asymmetric carbon atoms in the γ-lactone ring, so There are two types of diastereomers.These have structures that meet the purpose of suppressing the free rotation of the dipole part, so they can be used alone or as a mixture to produce liquid crystals. It is useful as a sexual compound.

Compound (A) according to the present invention can be produced by the following method.

(In the formula, the signs R1 and * have the same meanings as the signs R1 and * in formula (A)); It is synthesized by reacting a β-ketoester derivative represented by an alkyl group (R5 represents a lower alkyl group) or a malonic acid ester derivative in an organic solvent by adding a base.

The optically active glycidyl ether of formula (B), which is the above raw material compound, is prepared by the following method (in the formula, R1
The symbols and * have the same meanings as the symbols R1 and * in formula (A>) It is obtained by reacting the phenol derivative represented by R10 above with optically active epichlorohydrin in the presence of a base. The amount of optically active epichlorohydrin is preferably 1 to 10 equivalents based on the raw material phenol derivative, and the base used in the reaction is preferably 1 to 10 equivalents based on the raw material phenol derivative.
~5 equivalents are preferred. As a base, sodium hydroxide,
Examples include potassium hydroxide and potassium t-butoxide. Although the reaction can be carried out smoothly without a catalyst, quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide,
A catalyst such as benzyltrimethylammonium chloride or benzyltrimethylammonium bromide can also be added in an amount of 0.01 to 0.1 equivalent to the raw material phenol derivative. Optically active epichlorohydrin can be reacted as a solvent, but if necessary dimethylformamide.

Dimethyl sulfoxide, dimethyl acetamide.

Polar solvents such as acetonitrile, t-butyl alcohol and water can also be used. The reaction temperature is 50-80℃
It will be completed in 1 hour 0.5 to 3 hours.

In addition, as a method different from the above method, a raw material phenol derivative and optically active epichlorohydrin are reacted in the presence of an amine such as morpholine, piperidine, pyridine, etc. in an amount of 0.1 to 0.5 equivalent to the phenol derivative as a base. to form an optically active chlorohydrin, and add 1 to 5
There is a method of reacting an equivalent amount of a base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium t-butoxide, etc. to obtain a glycidyl ether by ring closure. Although this method is a two-step reaction, it has the advantage of easy extraction operation. In this case, the reaction is 50-8
The process is completed in 3 to 24 hours at 0°C.

Racemic glycidyl ether can be obtained by using racemic epichlorohydrin. As for optically active epichlorohydrin as a raw material, eight highly purified ones are disclosed in JP-A-61-1 filed by the present applicant.
32196@ and Japanese Patent Application Laid-Open No. 62-6697, and the eight bodies obtained by the method described in Japanese Patent Application 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 6 below, R3 is R in formula (A) above.
Rγ represents the same group as 3, and Rγ represents a hydrogen atom or an alkyl group having one fewer carbon atoms than R3.

In Table 6, ph represents a phenyl group and R' represents a lower alkyl group.

That is, 4-(4-trans alkylcyclohexyl)
Phenol, 4-(4-alkyloxyphenyl)phenol, and 4-(4-alkylphenyl)phenol can be synthesized by known methods according to the synthetic routes shown in Table 1.2.3.

Furthermore, 4-(5-alkyl-2-pyrimidinyl)phenol and 4-(5-alkyloxy-2-pyrimidinyl)phenol are disclosed in JP-A-61-189274;
According to the method described in DE-NO144,409, each Table 4
, 5 can be synthesized by the synthetic route.

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 shown in Table 6, compound (E) is synthesized by protecting the hydroxyl group of p-hydroxybenzonitrile by benzylation and converting the cyano group to amidine hydrochloride by a conventional method. 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-toluenesulfonic acid ester, or an alkyl methanesulfonic acid ester, and then with diethyl carbonate. A diethyl malonate derivative (G) is synthesized by reacting in the presence of a base.

Amidine hydrochloride (E) and diethyl malonate derivative (G)
and are condensed using a base such as sodium ethoxide or sodium methoxide, and then reacted with phosphorus oxychloride in the presence of a base such as N,N-diethylaniline, pyridine, 4-N,N-dimethylaminopyridine, etc. 4-[5-(4-alkyloxyphenyl)-2-pyrimidinyl]phenol (
Synthesize I).

Diethyl malonate derivative (G) during the synthesis of the above (I>)
Diethyl p-alkylphenylmalonate (F) instead of
When (E) and (F) are reacted according to the synthesis reaction process (I> using (E) and (G) as raw materials), 4-
(5-(4-alkylphenyl)-2-pyrimidinyl)
Phenol (H) can be synthesized.

Diethyl p-alkylphenylmalonate (F) used in this case can be synthesized by converting p-alkylacetophenone into a phenyl acetic acid Mm conductor by Willaerodt reaction, esterifying it with a lower alcohol, and condensing it with diethyl carbonate.

When producing the target compound (A) of the present invention, the compound (
B) and 1 to 5 equivalents of compound (C) or compound (D>
and refluxing with 1 to 5 times a base in an organic solvent for 1.5 to 24 hours.

The base used at this time is sodium methoxide,
Preferred are sodium ethoxide, potassium t-butoxide, sodium hydride, lithium hydride, n-butyllithium, etc., and organic solvents include alcohols such as methanol, ethanol, and t-butyl alcohol, tetrahydrofuran, ethyl ether, and dimethoxyethane. .

Preferred are ethers such as diethylene glycol dimethyl ether and dioxane, aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide, or mixed solvents thereof.

In addition, in the above method, when R4 of compound (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 to obtain the target compound ( A> is obtained.The solvent used is dimethylformamide.

Dimethylacetamide, dimethyl sulfoxide.

Polar solvents such as hexamethylphosphoric 1-lyamide, diethylene glycol dimethyl ether, and dioxane are preferred, and inorganic salts include 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.

The liquid crystal compound of the present invention can be obtained in a racemic form by using racemic epichlorohydrin as a raw material,
This compound can be added to other optically active liquid crystal compounds to adjust their helical pitch. Furthermore, the liquid crystal 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 crystal compound of the present invention can also be used for the following purposes.

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

(2) Display element using cholesteritter nematic phase transition effect (J, J, Wysoki, A, 8dams
and W.

Haas: Phys, Rev. Lett, 20.
1024 (1968)).

(3) Display elements using White Tiller type guest-host effect (D, L, White and G, N,
Taylor ;j, 8po1. Phys, 45.4
718 (1974)).

(4) immobilizing the cholesteric phase in the matrix;
Utilizing its selective scattering properties, it is used as a notch filter or bandpass filter (F, J.

niahn: Arit)1. PhVs, Lett.
, 18.231 (1971)).

(5) Circular polarization beam splitter (S, D, Jacob; 5PI) that utilizes the circular polarization characteristics of the cholesteric phase
E, 37.98 (1981)).

EXAMPLES The compounds according to the present invention, their production examples, and usage examples will be specifically explained below with reference to Examples, but the present invention is not limited by these Examples.

(Example) In each of the following examples, the R, S designation of the optically active compound (A>) of the present invention was performed based on the position number of the following chemical formula.

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゛Crystal phase SmA, smectic A phase SmC, smectic C phase SmC” chiral smectic C phase Sml;
Unidentified smectic phase N other than SmA, SmC, SmC''; Nematic phase; Chiral-nematic phase I: Isotropic liquid phase Chiral smectic C phase (SmC'') is further confirmed by measuring the dielectric constant. did.

Synthesis of phenol derivative> Production example 1 4-[5-(4-n-octyloxyphenyl)-2
-Synthesis of pyrimidinylcotenol i) Synthesis of 4-benzyloxyphenylamidine hydrochloride 4-cyanophenol 95.2U, benzyl chloride 1
27g, potassium carbonate 138g in acetone 160d
The mixture was refluxed under stirring for an hour. The product was filtered off, concentrated under reduced pressure,
Benzene was added, washed with water, and the benzene was distilled off under reduced pressure to obtain 4-
141.380 benzyloxybenzonitrile was obtained.

Next, 141 g of 4-benzyloxybenzonitrile,
Dissolved in 338 parts of benzene, added 270 parts of ethanol, and cooled to 0°C. After blowing 36.0 parts of hydrogen chloride gas into the resulting slurry solution while stirring, the liquid temperature was raised to 25°C and left for 2 days. .

The reaction mixture was concentrated to ⅓ under reduced pressure, ether was added to the concentrated solution, and the precipitated crystals were filtered with suction to obtain 183 g of imide ester.

183 g of the above imide ester was made into a slurry solution with 270 d of ethanol, an ethanol 405rd solution of 60.75 CI of ammonia gas was added thereto, and after being left at air temperature for 2 days, the solvent was distilled off under reduced pressure and the 4-benzyloxyphenylamidine salt rli 164.5o of salt was obtained.

NMR (DMSO-d6) δ:5.19 (2H,S) 7.17 (2H,d, J=9.0H2)7
．． 35 (5H,s) 7.86 (2H,d) ii) Synthesis of diethyl 4-n-octyloxyphenylmalonate 50.013 of 4-hydroxyphenylacetic acid was dissolved in 40 (7!) of ethanol, and 0.5 mff of Ia sulfuric acid After stirring under reflux, ethanol was distilled off to obtain 60 (l) of ethyl 4-hydroxyphenylacetate.

Next, 59 g of ethyl 4-hydroxyphenylacetate.

221 words of sodium ethoxide to 150 rn of ethanol
Add 63.51 J of n-octyl bromide, stir under reflux for 3 hours, concentrate the reaction solution under reduced pressure, add ethyl acetate to dissolve the oil, wash with water, dry over anhydrous magnesium sulfate, Ethyl acetate was distilled off under reduced pressure, and ethyl 4-n-octyloxyphenylacetate was obtained by distillation under reduced pressure.79.
6g was obtained. (bρ179℃10.1 city] 1g) Thus obtained ethyl 4-n-octyloxyphenylacetate 79g 1 ethanol 140d1 diethyl carbonate 300g
/d and 19.3 g of sodium ethoxide were mixed and heated and stirred while distilling off 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 (J) of diethyl 4-n-octyloxyphenylmalonate.

NMR (CDC13) δ: 0.5-2.0 (21H, m) 3.90
(2H, t, J=6.0H2)4.16
(4H, Q, J=7.2NZ >4.52
(IH, S> 6.80 (2H, d, J=9.0Hz>
7.26 (2H, d, J=9.0Hz)
iii) Synthesis of 4-[5-(4-n-octyloxyphenyl)-2-pyrimidinylcotenol 4-benzyloxyphenylamidine hydrochloride 65.6 g, 4-
Diethyl n-octyloxyphenylmalonate 91.0
(] was dissolved in methanol 5007, sodium methoxide 44.89 was added, and the mixture was stirred under reflux for 9 hours. After cooling, the reaction mixture was acid-proofed with Wt acid, and the precipitated crystals were collected by suction filtration and yellow crystals 77, 7Q were added. It's 19.

77 g of the above yellow crystals and 310 ml of phosphorus oxychloride 1°N,
N-diethylaniline 46.5Ird! The mixture 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 crude product 70Q. This was recrystallized from ether to obtain 21 g of a compound represented by the following chemical formula.

NMR (CDCj!3) δ: 0.4-2.1 (15H.

3.99 (2 days.

5.09 (2H.

6.7-7.5 (11H.

8.38 (2@.

m) t, J=a, ouz 'I S) m) d, J=9.0H7) The above colorless crystal 19.8! II, ethanol 757rnf
! , Magnesium II chloride 11.4 (J, water 577.1
4 g of 0% Pd-C was heated for 60 minutes until the theoretical amount of hydrogen was absorbed.
The mixture was heated and stirred at ℃ under a hydrogen atmosphere. The reaction mixture was filtered under suction, and the desired 4-[5-(4-n-octyloxyphenyl)-2-pyrimidinyl]phenol was obtained from the filtrate.7.
7g was obtained.

mp 137℃ NMR (CDα3) δ: 0.5-2.1 (15H, m>4.00
(2H, t, J=6.0H2)6.92
(2H, d, J=9.OH2)7.01
(2H, d, J=9.0H2)7.50
(2H, d, J=9.0Hz >8.30
(2H, d, J=9.0H2)8.94
(2H,s) <Synthesis of compound of formula (B)> As the raw material optically active epichlorohydrin, JP-A-61-
No. 132196, JP 62-6697@ and patent application 1983
The material manufactured by the method described in No. 2-283393 was used. These substances are R-(-) and S
-(10)-Epichlorohydrin, each has a chemical purity of 98.5% or more and an immunological purity of 99% or more according to gas chromatography analysis (the specific optical rotation is "α").
"Tube=-34.0", +34.0°; C=1.
2. methanol).

Synthesis Example 1 5.55 g of R-(-)-epichlorohydrin and 2.46 g of 4-(trans-4-n-pentylcyclohexyl)phenol represented by the following chemical formula (1°n-C
s H1t >OH While stirring a mixture with 0.04 g of benzyltriethylammonium chloride at 60°C, an aqueous sodium hydroxide solution (NaOHO, 45 (II, 15 m of water) was added dropwise over 20 minutes, and the mixture was heated at a distant flow for approximately 1 hour. The reaction solution was cooled to room temperature, extracted with ether twice, washed once with saturated brine, and the solvent was distilled off under reduced pressure.The residue was purified by silica gel column chromatography to give the following chemical formula ( S)-2,3-epoxyprobyl 4-(trans-
1.8 g of 4-n-pentyl Schiff[1hexyl)phenyl ether were obtained.

[α] Pipe +4.44° (C=1.36. CH2(1
'2) NMR (CDα3) δ: 0.45~2.50 (21H, m>2.50~
3.00 (2H, m> 3.15 ~ 3.50 (IH, m> 3.70 ~ 4.30 (2t (, m) 6.79
(2H, d, J=9.0Hz)7.09
(2t-1, d, J = 9.0 Hz > Synthesis Example 2 2.50 g of a compound represented by the following chemical formula as a raw material phenol derivative, n -Ce H1y +OH Same R-(-)-epichlorohydrin as in Synthesis Example 1 4.2
59 and benzyltriethylammonium chloride 20
Dissolve mg in dimethylformamide 3d, and add 24% sodium hydroxide aqueous solution (1.2%) at 60°C.
It went up and down. 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 (l of 8 glycidyl ethers represented by the following chemical formula at 1 gmp 90°C [α] v + 4.44° (C = 1.01. CH2C
1C12)N (CDC13) δ: 0゜50~3.00 (191-1, m) 3.1
0-3.50 (IH, m) 3.80-4.30 (2H, m> 6.75-7.60 (8 days, m> Synthesis Example 3 Compound 10. 0(1, n-CaHtyO((〒〒:;:]〉-1-→に】〒〒
: 18.69 mg of R-(-)-epichlorohydrin, same as in OH synthesis 1. 367 mg of piperidine and 1 rnl of dimethylformamide were mixed and stirred at 60°C for 10 hours. The solvent was distilled off from the reaction solution under reduced pressure. 5ml acetone
was added, and while stirring at room temperature, a 24% sodium hydroxide aqueous solution (1.2 equivalents) was added dropwise to react 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 1.5 Ml of 8 glycidyl ethers represented by the following chemical formula! ! Ta.

mp 131℃ [α]Ll−3,03° (C=0.55. CH2C
f12) NMR (CDα3) δ: 0.70 to 2.20 2.55 to 3.00 3.15 to 3.45 3.75 to 4.20 (17H, m> (2H, m> (IH, m > (2H, m) 6.89 (2H, d, J=9.OH2)
6.92 (2H, d, J=8
．． 4Hz >7.43 (4H, d, J
=9. OH2) Synthesis Example 4゜ Compound 5.280, n -C3H7() () (S)-(+)-Epichlorohydrin 11.5!I as a raw material phenol derivative
I.J.

3.00 g of potassium t-butoxide and 45 d of t-butyl alcohol were mixed and stirred at 60°C for 3 hours.

After removing the solvent from the reaction solution under reduced pressure, extraction with chloroform was performed, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain 8 glycidylny [α] i −5,71° represented by the chemical formula below.
(C=1.66, CH2α2) NMR (CDC13) δ: 0.60-2.50 (171-1, m>2.6
0-2.95 (2H, m) 3.15-3.60 (IH, m> 3.80-4.30 (2H, m> 6.76 (2)-1, d, J=8.4H
z >7.07 (2H, d, J=8.4
Hz > Synthesis Example 5 Eight glycidyl ethers represented by the following chemical formula were obtained in the same manner as Synthetic Leather Example 4 except that compound n-CI283() (Xo H ) represented by the following chemical formula was used as the raw material phenol derivative.

mp 91°C [(X] Electron-3,59° (C=1.07.CH2
Cb) NMR (CDC1x) δ: 0.85-2.93 (27H, m>3.34-
3.40 (IH, m>3.97~4.27
(2H,rrl)6.94-7.53 (8H,m) Synthesis Example 6 Compound 10(1) shown by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin 16.
070.20% by weight sodium hydroxide aqueous solution 7.33g
and dimethylformamide 2M at 60-70°C.
The mixture was heated and stirred for 1 hour. After cooling the reaction solution, water was added and the product was extracted with dichloromethane to obtain crude product 11.
．． 67g was obtained. The crude product was purified by silica gel column chromatography to obtain 8 glycidyl ethers 9.070 represented by the following chemical formula.

mp 74℃ [α]τ+1.66° (C=1.02.CH2α2)
NMR (CD(f'3) δ: 0.5-2.2 (15H, m) 2.6-3.
0 (2H, m> 3.1~3.7 (IH, 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 7 Compound 7.44 shown by the following chemical formula obtained in Production Example 1 of the phenol derivative as a raw material phenol derivative
g, R-(-)-1 picchlorohydrin 9.1 as in Synthesis Example 1
6a, 50% by weight aqueous sodium hydroxide solution 1.74 (1
and dimethylformamide 77d at 60 to 70
Stirred at ℃ 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 the product represented by the chemical formula 8 below.
6.90 g of glycidyl ether was obtained.

mp 198℃ [α] tube +〇, 95° (C=1.04.CH2α2)
NMR (CDC13) δ: 0.6-261 2.6-3.0 3.2-3.5 3.8-4.5 6.99 7.50 8.40 8.90 (15H, m> ( 2H, m> (IH, m> (2H, m> (4H, d, J=9.0Hz > (2H, d,
J=9.0Hz>(2H,d, J=9.0Hz>(2H,s) Synthesis Example 8 Compound 1.01C1 shown by the chemical formula below as a raw material phenol derivative, R-(-)- same as Synthesis Example 1 epichlorohydrin 2.0
1 g and benzyltriethylammonium chloride 16
mg were mixed and heated to 70°C, and 650 mg of a 24% by weight aqueous sodium hydroxide solution was added dropwise thereto. 2 at 70℃
After stirring for an hour, the reaction solution was allowed to reach room temperature, then extracted three times with chloroform and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from hexane to obtain 380 mg of 8 glycidyl ethers represented by the following chemical formula.

mp 65℃ [α]V+1.90" (C=0.46. CH2C
f12) NMR (CDα3) δ: 0.6-3.0 (19H, m) 3.2-3.
6 (IH, m> 3.9~4.5 (2H, m) 6.99 (21-1, d, J=9.0Hz
)8.36 (2H, d, J=9.0Hz
>8.55 (2H,S) Synthesis Example 9 Compound 3.12(] shown by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin 4.6 as in Synthesis Example 1
27q, 50 wt ω% sodium hydroxide aqueous solution 0.88Q
and dimethylformamide 30d at 60°C.
．． The mixture was heated and stirred for 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 8 glycidyl ethers represented by the following chemical formula.

The specific optical rotations of glycidyl ethers are summarized in Table 7.
It was shown to.

In addition, in Table 7, the signs of R3, n, X and * are based on the following chemical formula.

mp 65℃ [α]V+2.47° (C=1.02. CH2Cf
12) NMR (CDC13) δ: 0.6-2.0 (19H, m>2.4-3.
0 (4H, m) 3.2~3.5 (IH, m) 3.8~4.5 (2H, m> 6.98 (2H, d, J=9.0Hz
>8.33 (2H, d, J=9.0H2
)8.53 (2 days, s) Synthesis Example 10~
1] Table 7 shows the specific optical rotations of optically active glycidyl ethers synthesized by the same method as in Synthesis Examples 1 to 9.

Optical Activity Tables Obtained in Synthesis Examples 1 to 9 Example 1 After washing 50 wt % sodium hydride (224 ml) suspended in mineral oil twice with dry ether, 10 d of dry tetrahydrofuran (1 furan) was added. While stirring this suspension at 40°C, methyl 3-oxododecanate i,org was added dropwise and stirred for 5 minutes, followed by (S)-2 obtained in Synthesis Example 1.
, 3-epoxypropyl 4-(trans-4-n-pentylcyclohexyl) phenyl ether i, 4ig was added dropwise thereto, and the mixture was stirred under reflux for 20 hours. After the reaction solution was returned to air temperature, 4N hydrochloric acid was added dropwise until p11=1, then ether extraction was performed twice, washed once with saturated brine, and the solvent was distilled off under reduced pressure. The residue was separated and purified by silica gel column chromatography and is represented by the following chemical formula (2S).

43) body: 430 mg of a T-lactone derivative consisting of a mixture of (2R,43) body = 50:50 was obtained.

Physical properties phase transition temperature of (2R,4S) body (23,43) dormant mixture [(r]L+-18,1° (C=1.06.CHC
f3) NMR (CD(1'3) δ: 0.87 to 1.86 (39t-1, m) 2.2
6-3.06 (3H, m) 3.73-4.21 (3H, m) 4.85-4.90 (IH, m> 6.82 (2H, d, J=8.54Hz>
7.12 (2H, d, J=8.551f
z) I R (K B r ) 1778.1720
Cm-1 (2R,4
3) Physical properties of polyester (23,43) body mixture with a thickness of 50 μm Phase transition temperature [α]″g+13.3° (C=1.09. CH(J
! 3) NMR (CDCI13) δ: 0.87-1.88 2.20-3.09 3.72-4.21 4.77-4,99 6.81 7.10 IR (KBr) Example 3 Implementation Methyl-3-oxododeca (33H) in Example 1
,m) (31tm) (3 days, m> (IH,m) (2H,d, J=8.55Hz> (2H,d, J=8.55tlz) 1762, 1716Cm-1 Spacer with tyrene brephthalate film The cell is sealed in a cell made of nether glass, applied with an alternating current of 70H2, and the dielectric constant is measured using the bridge method.
Shown in the figure. This revealed that this material exhibits a ferroelectric phase. In addition, when the dielectric constant of γ-lactone M1 obtained in Examples 2 to 4 below was measured in the same manner, substantially the same result was obtained as 1q.

Example 2 The chemical formula shown below was prepared in the same manner as in Example 1 except that 1.14 g of methyl 3-oxo-nonanate was used instead of methyl 3-oxo-dodecanate.
2R,43) form: (23,43) form -50: 970 mg of a γ-lactone derivative consisting of a mixture of 50 was obtained.

(2R,48) Dimethyl n-butylmalonate 130mg instead of dinate
The procedure was the same as in Example 1 except that γ-lactone derivatives of the (23.43) form and (2R,43) form represented by the following chemical formulas were used at 50 m9 and 40 mg4%, respectively.

(23,43) Closed phase transition temperature c8 L→I [α] 9 + 33.45° (C= 0.658.
CH2α2) NMR (CD(j!3) δ: 0.88-1.98 2.38-2.67 4.07-4.13 4.67-4.73 6.83 7.12 IR (KBr> (30H, m> (3 days, m) (2H, m> (IH, m> (2H, d, J=8.3H2) (2H, d, J-4,3tlZ) 1762 cm-1 Elemental analysis (02B84003 ) C Theoretical value (%) 77.95 Actual value (%) 77.91 (2R,4S) body 10.0? 10, 12 Phase transition temperature C85''C→I +20.37° at [α] (C =1.05.CH2C
f12) NMR (CDα3) δ: 0.70-2.95 (33H, m) 4.00-
4.25 (2H, m) 4.50~4.95 (IH, m> 6.77 (2H, d, J=8.4H2) 7
．． 11 (2H, d, J=8.4H2)IR
(KBr > 1762 cm-1 Example 4 163 m of 50 wt% sodium hydride suspended in mineral oil
Add 3d of dry 1,2-dimethoxyethane to 0 and stir at room temperature, then dimethyl n-butylmalonate. 1611
1J of 1,2-dimethoxyethane solution [3ml was added dropwise over 10 minutes. After further stirring for 5 minutes, a 1.2-dimethoxyethane solution containing 940 m0 of (S)-2,3-epoxypropyl-4-(trans-4-n-pentylcyclohexyl) phenyl ether obtained in Synthesis Example 1 was added to the reaction solution. 4m
1 was added dropwise over 10 minutes and stirred at high speed for 2.5 hours. After the reaction solution was returned to room temperature, 4N hydrochloric acid was added dropwise until the pH reached 1, followed by ether extraction twice, washing once with saturated brine, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 130 mg of a (23.43) γ-lactone derivative represented by the following chemical formula.

(23,43) Body phase transition temperature C - further 1 → I [α] tube + 27.61° (C = 0.039. CH
2Cb) NMR (CDα3) δ: 0.78-2.82 3.97-4.19 4.40-4.82 6.77 7.08 IR (KBr> Example 5 Optical properties obtained in Synthesis Example 1 The activated glycidyl ether, i.e. (S)-2,3-epoxypropyl 4-(trans-
370 ma of 4-n-pentylcyclohexyl)7phenyl ether, 151 mg of potassium t-butoxide, 357 mg of dimethyl methylmalonate and 3 InIl of t-butyl alcohol were mixed and stirred at high speed for 8 hours. After returning the reaction solution to room temperature and adding 4N hydrochloric acid dropwise until I)H=1,
Ether extraction was performed twice, then washed once with saturated saline, and the solvent was distilled off under reduced pressure (39H, m> (2H, m> (IH, m) (2H, d, J=8.4H2) ( 2H, d, J=8.4H2) 1758 cm-1 was removed.The residue was separated and purified by silica gel chromatography to obtain the (23.4S) body and (2R,
43) 60 mg and 50 mg of T-lactone derivatives respectively.

(2S, 4S) Body phase transition temperature [α]V+14.03” NMR (CDα3 δ: 0.88 0.97-1.84 2.39 2.49-2,56 2.69-2,76 4. 04~4.12 4.65~4.71 (C= 0.493. CH2α2) (3H, t, J= 7.0H2) (21H, m) (IH, t, J= 12.2H2) (IH ,m) (IH,m) (2H,m> (IH,m) 6.83 (2H,d, J= 8.7Hz
) 7.11 (2 days, d, J= 8.7
H2) IR (KBr) 1760cm-1M5
m/e (relative intensity 1%) 359 ((M+1), 26).

358 (M, 100) Theoretical value as 023H3403 358.2509 Actual value 358.2537 (2R, 43) Body phase transition temperature c 10 bar L → I [α] V +20.25° (C = 0.490.
CH2(1'2) NMR (CDα3) δ: 0.89 (3H, t, J = 6.8H
z>0.97~1.40 (17H, m) 1.84
(3H, d, J=10.7Hz) 2.02~
2.10 (IH, m) 2.39 (1N, t, J=12.
2Hz>2.45~2.51 (ll-1,m)2.
87~2.93 (1N, m>4.01~4.12
(2f-1, m>4.76~5.03 (IH,
m> 6.79 (2H, d, J= 8.6H2
)7.11 (2H, d, J= 8.6H
2) IR (KBr) 1760cm-1M5m
/e (relative intensity 1%) 359 ((M+1), 26).

358 (M, 100) Example 6 The optically active glycidyl ether obtained in Synthesis Example 4, i.e. (R>-2,3-epoxypropyl 4-(trans-
4-n-propylcyclohexyl) phenyl ether 4
16mo, 188m of potassium t-butoxide (II, 443mc+ of dimethyl methylchloride, and 2.5d of t-butyl alcohol were mixed and stirred under reflux for 2 hours. The reaction solution was returned to room temperature, and 4N hydrochloric acid was added dropwise until pH = 1. After that, chloroform extraction was performed three times, and then the solvent was removed under reduced pressure by washing once with saturated saline.The residue was separated and purified by silica gel chromatography to obtain γ-lactone gi4 compound represented by the following formula. 77 mg of the (2R,4R) isomer and 86 mg of the (2S, 4R) isomer were obtained.

(2R, 4R) Body (2S, 4R) Body Phase Transition Temperature Phase Transition Temperature [α] l -16,82°NMR (CDα3 δ: 0.6~3.0 4.0~4.2 4.4~ 4.95 6.76 7.10 IR (KBr) (C=0.98. CH2Cl2) (23H, m> (2H, m> (IH, m> (2H, d, J= 8.0Hz) (2H ,d, J= 8.0Hz> 1762cm-1 [α] IF-27,82° (C=1.03.CH2
α2) NMR (CDα3) δ: 0.65-3.0 (23H, m>4.0-4
．． 2 (2H, m> 4.6~5.0 (IH, m> 6.76 (2H, d, J= 8.0H2
)7.10 (2H, d, J= 8.0H
z>IR(KBr) 1762 cm-1 Examples 7-11 Optically active T-lactone derivatives as shown in Table 8 were synthesized by the same method as in Examples 1-6.

Example 12 In Synthesis Example 4, 8 glycidyl ethers 380
mg, dimethyl malonate 274m (J, potassium (-
163 mg of butoxide and 2 d of t-butyl alcohol were mixed and stirred at high speed 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 column chromatography to obtain 220 mg of a 4H methoxycarbonyl-γ-lactone derivative represented by the following formula.

I R (K B r ) 1781.1744
crt 200 mg of the γ-lactone derivative of the above formula, 232 m0 of magnesium chloride. Dimethylacetamide 1.5d
and 0.5-liter of water were 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 γ of the 4H form shown by the following formula.
-Lactone derivative 145 phase transition temperature C-W Rainbow→I [α] Sweetened 18.64° (C=1.27.CH2α2
) NMR (CDα3) δ: 0.65-3.45 (21H, m>3.90-
4.30 (2H, m> 4.55~5.00 (tH, m) 6.77 (2H, d, J=9.0Hz>
7.11 (2H, d, J=9.OH2)I
R(KBr>1778cnr1 Above Example 7~
The measurement results of the phase transition temperature of the optically active γπ lactone derivative obtained in Example 12 are summarized in Table 8 together with Examples 1 to 6.

Example 13 8 glycidyl ethers obtained in Synthesis Example 2 370m
442 mg of diethyl n-propylmalonate, 134 mg of potassium t-butoxide, and 3 d of t-butyl alcohol were mixed and stirred under reflux for 10 hours. The reaction solution was returned to room temperature and adjusted to pH=1 by adding 4N hydrochloric acid, and then washed with water and methanol to obtain white crystals. This was separated and purified by silica gel chromatography to obtain a γ-lactone derivative (2S) represented by the following formula.

240 mg of the 4S) body and 140 mg of the (2R,4S) body were obtained.

(2S, 43) Body phase transition temperature C11 L→I [α] 'ft +32.67° (C= 1.081
．． CH2 (J2) NMR (cDC!13) δ: 0.70-3.00 (27H, m) 4.00-
4.25 (2H,m> 4.40~4,85 6.60~7.60 IR(KBr>(2R,4S) body(IH,m>(8H,m) 1762Cm-1(C=O) Phase transition temperature C117'C→I [α] tube +22.50" (C= 0.504.C
H2C1C12)N (CDCIl3) δ: 0.70-3.00 4.00-4.25 4.50-5.00 6.60-7.60 IR (KBr> Example 14 Obtained in Synthesis Example 3 260 questions of 8 glycidyl ethers, 269 mg of dimethyl n-octylmalonate, 9 omg of potassium t-butoxide, and 271-
1,m) (2H,m) (IH,m> (8H,m) 1762cm-' (C=0) Cole 2m7!il- were mixed and stirred under reflux for 13 hours. The treatment after the reaction was the same as in Example 13. This was separated and purified by silica gel chromatography to obtain a T-lactone derivative (23,4
S) 43 mg of body was 1q.

Using the obtained 8 glycidyl ethers, the (2R,4R) and γ-lactone derivatives were prepared in the same manner as in Example 13, except that n-butyl dimethyl malonate was used instead of n-propyl diethyl malonate. (23,4R) body was obtained.

(2R, 4R) Body phase transition temperature C13B→I [cr] 1r+28.59° (C= 0.674.
C)-12C1C12)N (CDCIl3) δ: 0.70~2.95 (37H, m) 3.80~
4.20 (,4H,m)4.45~4.90 (
IH, m> 6.90 (4H, d, J=9.0Hz>
7.42 (4H, d, J=9.OH2)I
R(KBr> 1760cm-1 Example 15 As an optically active glycidyl ether in Synthesis Example 5, the phase transition temperature C-Eva L→I [α]-28,56° (C=1.06. CH2C
J12) NMR (CDCIl: s > δ: 0.85-2.69 4.15-4.18 4.71-4.77 6.95-7.53 IR (KBr> (37H, m> (2H, m> (1H, m) (8H, m> 1764 cm-1 (2S, 4R) Body phase transition temperature 012 BA L→■ [α] IF -22,98° (C=1.07.C
H2C1C112)N (CDC13) δ:0.85~2.85 (37H, m>4.08~
4.21 (2H, m) 4.81~4.86 (IH, m> 6.93~7.52 (8H, m> IR (KBr) 1760 cm-1 Example 16~
22 Optically active γ-lactone derivatives as shown in Table 9 were synthesized by the same method as in Examples 13 to 15.

Example 23 Eight compounds obtained in Synthesis Example 10 as optically active glycidyl ethers 365mc+, dimethyl malonate 232
mCl and potassium t-butoxide 138m (4 expressed by the following formula in the same manner as in Example 12 except that II was used)
226 mg of 8 2-(methoxycarbonyl)-γ-lactone derivatives (q).

IR(KBr) 1740.1768Cm-1
Next, the γ-lactone derivative represented by the above formula was prepared in Example 1.
Hydrolyzed and decarboxylated in the same manner as 2 to obtain 48 shown by the following formula.
145 mg of the γ-lactone derivative of the body was measured at the phase transition temperature CI3 nail L→I [(X] f +19.16° (C=1.03.
CH2Cf12) NMR (CDC13) δ: 0.80~1.75 (11H, m>2.15~
2.85 (6H, m> 4.05-4.30 (2H, m> 4.75-4.95 (IH, m> 6.85-7.60 (8H, m> IR (KBr) 1764 cm- 1 The measurement results of the phase transition temperatures of the optically active γ-lactone derivatives obtained in Examples 16 to 23 are summarized in Table 9 together with Examples 13 to 15.

Example 24 Eight glycidyl ethers obtained in Synthesis Example 7 518m
g,n-Okjiru? 1170 mg of dimethyl lonate and 269 mg of potassium t-butoxide were dissolved in 5 dimethyl formamide and 511 i1 of t-butyl alcohol.
The mixture was heated and stirred at ℃ for 5 hours. The treatment after the reaction was carried out in the same manner as in Example 13 to obtain a γ-lactone derivative 74 represented by the following formula.
2 mg was obtained. This compound is a mixture of diastereomers, and the (23,43) and (2R,43) forms were obtained by rough silica gel chromatography.

(23,43) Body phase transition temperature υ [α] tube + 19.45° (C = 0.613. CH
2CJ! 2) NMR (CDα3) δ: 0.4-3.0 3.7-4.3 4.71 7.00 7.50 8.39 8°89 IR (Nujol) (2R,4S) body (35H, m) (4H,m>(IH,m> (4H,d, J=9.0Hz>(2H,d, J=9.0Hz>(2H,d, J=9.0H2) (2H,S) 1778cm-1 Phase transition temperature [α] Kan+7.09° (C= 0.115. CH2
α2) NMR (CDα3) δ: 0.4-3.0 (35H, m>3.7-4
．． 3 (4H, m) 4.82 (1N, m> 7.00 (4H, d, J=9.0Hz
>7.50 (2H, d, J=9.0H2
) 8.39 (2H, d, J = 9.0 dragon) 8
．． 85 (2H, 5) IR (Nujol> 1778 cm-1 Example 2
5 1.0 g of 8 glycidyl ethers obtained in Synthesis Example 6
, dimethyl n-butylmalonate 1.056 (1, 63 mg of potassium t-butoxide was dissolved in dimethyl formamide 10
Dissolve in 10 d of d and t-butyl alcohol and heat at 90°C for 2
The mixture was heated and stirred for hours. The treatment after the reaction was carried out in the same manner as in Example 13, and 626 mg of the γ-lactone derivative (q.
A (2R,43) body and a (2R,43) body were obtained.

(2S.

4S) Body phase transition temperature C-Eva L→I [a] V + 41.04° (C= 0.137
°NMR (CDα3) δ: 0.4-3.1 3.9-4.3 4.66 6.92 8.25 8.35 IR (Nushor) (2R, 43) body (27H, m> (4H , m> (IH, m> (2H, d, J=9.OH2) (2H, d, J=9.OHz) (2H, S) ・1776CIII-1 CH2C122> Phase transition temperature 0 10 skin L→■ [α]′g+25.02° (C=0.23°NMR
(CDC13) δ: 0.4-3.1 3.9-4.3 4.77 6.92 8.25 8.35 IR (Nujol) Example 26 Obtained in Synthesis Example 9 as optically active glycidyl ether The (2S, 4S) and (2R, 4S) body was obtained.

CH2Cf12) (27t-1,m> (4H,m) (IH,m> (2H,d, J=9.0Hz) (2H,d, J=9.OH7) (2H,s) 1776cm-1 ( 23,43) Closed phase transition temperature C127'C→I [a] i +26.01° (C= 1.062.
CH2C1C112)N (CDα3) δ: 0.5 to 2.9 (49H, m>4.19
(2H, m) 4.82 (IH, m> 6.95 (2H, d, J=9.0H2)8
．． 32 (2H, d J=9.0Hz >8
．． 52 (2H, 5) IR (Nujol) 1778cm-1 (2R,
4S) Body phase transition temperature c88L→■ [α] i +17.12° (C= 0.398°N
MR (CDα3) δ: 0.5-2.9 4.19 4.81 6.95 8.32 8.52 IR (Nujol) Example 27 Eight glycidyl ethers obtained in Synthesis Example 8 320m
g, n-hexyl? Dimethyl phosphate 406 mg.

116 mg of potassium t-butoxide was dissolved in 3.5 Id of t-butyl alcohol and stirred at high speed for 6 hours. The post-reaction treatment was carried out in the same manner as in Example 13, and a mixture of diastereomers of the γ-lactone derivative ((23,43)/(2R,
43) = 9/1) 270+no was obtained.

CH2α2) (49H,m>(2H,m>(IH,m>(2H,d, J=9.0Hz>(2H,d, J=9.0Hz>(2H,S) 1778cnrl Examples 28-33 Optically active γ-lactone derivatives as shown in Table 10 were synthesized by the same method as in Examples 24-27.

The measurement results of the phase transition temperature of the optically active γ-lactone derivatives obtained above are summarized in Table 10 together with Examples 24 to 27.
It was shown to.

(2S.

43) Physical property phase transition temperature of rest (2R1 4S) mixture
(CDC13) δ: 0.50 to 2.80 4.10 to 4.25 4.45 to 4.85 6.95 8.34 8.52 IR (Nujol) (33H, m> (2H, m> ( IH, m) (2H, d, J = 9.0Hz > (2H, d, J = 9.0H2) (2H, s > 1778 cm-1 CH2CJ12) Example 34 Represented by the following chemical formula obtained in Example 32 It is a graph showing the relationship between temperature and dielectric constant of T-lactone derivative <23.4S) derivative (23,43>).

Claims (4)

[Claims] (1) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (R^1 in formula (A) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A group selected from
or 1, R^3 is an alkyl group having 1 to 15 carbon atoms, R^2
is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where 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 liquid crystalline compound having an optically active γ-lactone ring as shown below. (2) The compound according to claim 1, wherein the liquid crystal compound is a racemate. (3) General formula (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) (R^1 in formula (B) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups selected from, n or e, are each independently 0 or 1
, R^3 represents an alkyl group having 1 to 15 carbon atoms, and the symbol * represents an asymmetric carbon atom) and general formula (C) or (D) ▲ Numerical formula, chemical formula, table etc. ▼ (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (D) (In formulas (C) and (D), R^4 is a hydrogen atom or has a carbon number of 1 to 1.
General formula (A) characterized by reacting a β-keto ester derivative or a malonic acid ester derivative represented by (15 alkyl group, R^5 represents a lower alkyl group) by adding a base in an organic solvent. , chemical formulas, tables, etc. ▼(A) (R^1 in formula (A) is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups selected from, n or e, are each independently 0 or 1
, R^3 is an alkyl group having 1 to 15 carbon atoms, R^2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, m is 0 or 1, R^4
represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, *
The symbol represents an asymmetric carbon atom.) A method for producing a liquid crystalline compound having an optically active γ-lactone ring. (4) The method according to claim 3, wherein the liquid crystalline compound is a racemate.