JPH03173877A - Optically active glycidyl ether derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R<1> is formula II to IV (R<3> is 1-15C alkyl; n and e are 0 or 1); * indicates asymmetric carbon atom]. USE:Useful as a synthetic raw material for new liquid crystalline compounds. PREPARATION:A phenolic derivative expressed by the formula R<1>OH is reacted with an optically active epichlorohydrin in the presence of a base (e.g. NaOH or KOH) according to the reaction formula to afford the compound expressed by formula I. The optically active epichlorohydrin is used in an amount of preferably 1-10 equiv. based on the phenolic derivative and the base is used in an amount of preferably 1-5equiv. based on the phenolic derivative. An optically active liquid crystalline compound, obtained by using the aforementioned compound expressed by formula I and having the gamma-lactone ring has good stability to heat and water and excellent properties as a ferroelectric liquid crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an optically active glycidyl ether derivative that is a raw material for a novel liquid crystalline compound that can be used for display elements or electro-optical elements.

(Prior art and problems to be solved by the invention) Liquid crystals have come to be widely used as display materials, but
Currently, the display method is TN (Twisted N
ematic) 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.

Compelling liquid crystals were first discovered in 1975 by R.B. Meyer et al. (J. Phys.
sique.

36, L-69 (1975)), this device has excellent performance in that it has an extremely fast response speed and memory properties because the driving force is a relatively large force derived from spontaneous polarization, and it has been used as a new display element. Attention has been paid. 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. It is also necessary to have a dipole moment in the direction perpendicular to the long sleeve of the molecule.

The ferroelectric liquid crystal DOBAHBC synthesized by Mever et al. has the following structure and satisfies the above conditions, but it is chemically unstable because it contains a Schiff base, and its spontaneous polarization is 3xlO-9C/ cm
It was small. 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 [)OBAMBC is one position closer to the carbonyl group, has a spontaneous polarization of 5×10''8C/Cfi. and DOBAHBC
It is larger than. This is because the asymmetric carbon, which is an important element for the appearance of ferroelectricity, and the dipole position are close to each other, which suppresses the free rotation of the dipole part of the molecule and improves the orientation of the dipole. Conceivable. 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 satisfactory spontaneous polarization and high-speed response could not be obtained because the dipole part could not be fixed.

(Means for Solving the 0! Problem 5) The present inventors have proposed that, as a means for suppressing the free rotation of the dipole portion of conventional ferroelectric liquid crystal compounds, the asymmetric moiety is directly connected to the five-membered ring lactone. Free rotation is restricted by the structure,
Moreover, a novel liquid crystalline compound (A) having chemically stable ferroelectricity has been discovered, and the present invention provides a raw material compound for developing this compound.

The present invention is an optically active glycidyl ether derivative represented by the following formula (B).

(-In formula (B), R1 is a group selected from R3→O but %, R3→O is a group selected from 4), n or e is each independently O or 1, and R3 is a group having 1 to 15 carbon atoms. represents an alkyl group, and the symbol * represents an asymmetric carbon atom> Examples of the alkyl group for R3 above include methyl.

Ethyl, 0-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, °C-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
-Methylhexyl, 1-methylhexyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3
-Methylheptyl.

2-methylheptyl, 1-methylheptyl, 7-methyloctyl, 6-methyloctyl, 5-methyloctyl,
4-methyloctyl, 3-methylocdyl, 2-methyloctyl, 1-methyloctyl, 8-methylnonyl, 7
-Methylnonyl, 6-methylnonyl, 5-methylnonyl, 4-methylnonyl, 3-methylnonyl, 2-methylnonyl.

1-methylnonyl, 3,7-dimethyloctyl.

Groups such as 3.7.11-trimethyldodecyl may be mentioned.

The optically active glycidyl ether derivative represented by general formula (B) of the present invention can be produced by the following method.

It is obtained by reacting the phenol derivative shown in RIO above with optically active epichlorohydrin in the presence of a base. The amount of optically active shrimp chlorohydrin 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 proceeds 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.

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. 13219/1986, filed by the present applicant.
The method described in Publication No. 6 and Japanese Patent Application Laid-Open No. 62-6897,
As the three bodies, those obtained by the method described in JP-A-1-230567 can also 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 the formula (B) above.
represents the same group as R3, 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, d-(4-trans alkylcyclohexyl)
Phenol, /1-(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 E-No. 144,409, 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 shown in Table 6, compound (E) is synthesized by protecting p-hydroxybenzonitrile by benzylation of water M1 and converting the cyan group into amidine salt M salt by a conventional method. On the other hand, after esterifying p-hydroxyphenylacetic acid with a lower alcohol, the phenolic water M group is alkylated with an alkylating agent such as an alkyl halide, an alkyl D-toluenesulfonic acid ester, or an alkyl methanesulfonic acid ester, and then carbonic acid A diethyl malonate derivative (G) is synthesized by reacting with diethyl 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 1 phenol (
Synthesize I).

Diethyl malonate derivative (G) during the synthesis of (I) above
Diethyl p-alkylphenylmalonate (〉
When (E) and (F) are reacted according to the synthesis reaction process of (I) using (E) and (G) as raw materials, 4-
[5-(4-alkylphenyl)-2-pyrimidinyl 1
Phenol (b) can be synthesized.

Diethyl p-alkylphenylmalonate (") used in this procedure can be synthesized by converting p-alkylacetophenone into a phenylacetic acid derivative by Wil Igerodt reaction, esterifying it with a lower alcohol, and condensing it with diethyl carbonate. .

The following method can be used to produce the liquid crystal compound (A>) having a γ-lactone ring using the optically active glycidyl ether derivative of the present invention.

That is, an optically active glycidyl ether represented by (in the formula R
4 is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, R5 is a lower alkyl group), or a malonic acid ester derivative is synthesized by reacting it with a base in an organic solvent. Ru.

When producing the above compound (A), compound (B) and 1
This is achieved by refluxing ~5 equivalents of compound (C) or compound (D>) with 1 to 5 equivalents of a base in an organic solvent for 1.5 to 24 hours.The base used at this time is sodium methoxide. , sodium ethoxide, potassium t-butoxide, sodium hydride, lithium hydride, n-butyl lithium, etc. are preferable, and organic solvents include alcohols such as methanol, ethanol, 1-butyl alcohol, tetrahydrofuran, ethyl ether, dimethoxy. Ethane.

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 in compound (D>) is a hydrogen atom, after performing the above operation, add an inorganic salt and water under roughly neutral conditions and reflux in a polar solvent. A) is obtained.

The 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 1 to 10 equivalents of lithium chloride, sodium chloride, or potassium chloride.

Lithium bromide, sodium bromide, potassium bromide.

Lithium iodide, sodium iodide, potassium iodide,
Preferred are magnesium chloride, calcium chloride, strontium chloride, barium chloride, magnesium bromide, calcium bromide, barium bromide, magnesium iodide, calcium iodide, barium iodide, and the like. The amount of water added is 5-5
0 equivalents is preferred and the reaction is complete in 1 to 15 hours.

The optically active liquid crystal compound (A>) having a T-lactone ring obtained above can 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., Adams
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, T
aylor; J, Appl, Phys, 45.471
8 (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.

Kahn: Appl, Phys, Lett, .
18.231 (1971)).

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

(Example: Base of phenol derivative) Production example 1 4-[5-(4-n-octyloxyphenyl)-2
-pyrimidinyl] phenol synthesis 1) Synthesis of 4-benzyloxyphenylamidine hydrochloride 95.2 g of 4-cyanphenol, 1 benzyl chloride
2γ9. 138 g of potassium carbonate was refluxed in 160 ml of acetone for 5 hours with stirring. The product was filtered, concentrated under reduced pressure, benzene was added, washed with water, and the benzene was distilled off under reduced pressure.
-141.38 (l) of benzyloxybenzonitrile were obtained. Then 141 g of 4-benzyloxybenzonitrile was obtained.
Dissolve in 338ml of benzene and add 270ml of ethanol.
was added, cooled to O'C, hydrogen chloride gas was blown into the resulting slurry solution with stirring, and the liquid temperature was lowered to 25°C.
I left it 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, 60.75 (l) of ammonia gas solution in 405 d of ethanol was added thereto, and after standing at room temperature for 2 days, the solvent was distilled off under reduced pressure and 4-benzyloxyphenylamidine hydrochloride was added. 164.5 g of salt was obtained.

NMR (DMSO-da) δ: 5.19 (20, S) 7.17
(2nd, d, J=9.0)lz)7.35
(5th day, S) 7.86 (2nd day, d > 1i) Synthesis of diethyl 4-n-octyloxyphenylmalonate 4-hydroxyphenyl acid 1 50.0 (dissolve 1 in ethanol 400%, concentrate sulfuric acid 0 After stirring under reflux, ethanol was distilled off to obtain 60 (l) of ethyl 4-hydroxyphenylacetate.

Next, 59 g of ethyl 4-hydroxyphenylacetate.

22.4 g of sodium ethoxide was dissolved in 15 (7
and add n-octyl bromide 63.5 (].
After stirring at high speed for 3 hours, the reaction solution was concentrated under reduced pressure, ethyl acetate was added to dissolve the oil, washed with water, dried over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and 4- Ethyl n-octyloxyphenylacetate 79.6
(bp 179°C10, 1mm1+g> 79g of 4-n-octyloxyphenylacetate ethyl thus obtained, ethanol 140mf!, diethyl carbonate 3
00ml, mix 19.39ml of sodium ethoxide,
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 (CDCb) δ: 0.5 to 2.0 (210, m) 3.90
(20,t, J=6.0Hz)4.16
(4th, q, J=7.2H2) 4.52
(1st day, S) 6.80 <2nd day, d, J=9.0Hz
)7.26 (20,d, J=9.0Hz
)i) 4-[5-(4-n-octyloxyphenyl)
Synthesis of ~2-pyrimidinyl]phenol 65.6 g of 4-benzyloxyphenylamidine hydrochloride, 91.0 g of diethyl 4-n-octyloxyphenylmalonate, dissolved in 500 d of methanol, 44 g of sodium methoxide
．． After cooling, the reaction mixture was made acidic with sulfuric acid, and the precipitated crystals were collected by filtration under suction to obtain 77.7 g of yellow crystals.

The above yellow crystals 77 (l) and phosphorus oxychloride 310rdl.

46.57% of N,N-diethylaniline was centrifugally stirred 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 compound 21 (J is 14) shown by the following chemical formula.

NMR (CDCU3) δ 2O,4~2.1 15 t1. m)3.
99 20. t, J=6. )
5.09 20. S) 6.7~7.5 11 m
) 8, 38 2nd, d, J=9. OH
2) The above colorless crystal 19.8 (1, ethanol 757d,
Magnesium oxide 11.4g, water 57d, 10% Pd-
C4 (l) was 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 the desired 4-[5-(4-n-octyloxyphenyl) was extracted from the washings. 7.7 g of -2-pyrimidinyl 1-phenol was obtained.

mp 137°C NMR (CDα3> δ: 0.5-2.1 (150, m) 4.00
(20,t, J=s,oHz)6.92
2nd, d, J=9.0H2) γ, 01
2 to 1. d, J=9.0H
2) 7, 50 20. d, J=9.0
H2) 8.30 20. d, J=9.0
H2) 8.94 20. S><Synthesis of compound of formula (B)> As the raw material optically active epichlorohydrin, JP-A-611
No. 32196, JP-A-62-6697 and JP-A-12
A product manufactured by the method described in Publication No. 30567@ was used. These substances are R-(-) and S-(+)
-Epichlorohydrin, chemical purity is 98.5% or more and optical purity is 99% or more according to gas chromatography analysis (specific optical rotation is [α] back=-
34.0°, +34.0'; C=1.2. methanol).

Example 1 The above R-(-)-epichlorohydrin 5.55(] and
4-(trans-4-npentylcyclohexyl)phenol 2.46(], n-Cs shown by the chemical formula below
Mouth 11-〈)-＠-o To+benzyltriethylammonium chloride 0.04 (1) While stirring the mixture with sodium hydroxide aqueous solution (Mail 0
．． 45g of water and 15ml of water were added dropwise over 20 minutes, and the mixture was subjected to distant current for 1 hour. Cool the reaction solution to room temperature,
Ether extraction was performed twice, washed once with saturated brine, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography fid4 to obtain (S)-
1.8 g of 2,3-epoxypropyl 4-(trans-4-n-pentylcyclohexyl) phenyl ether was obtained.

[α tube +4.44° (C=1.36°NMR (C
Dα3> δ: 0.45-2.50 2.50-3.00 3.15-3.50 3.70-4.30 6.79 (210, m) (20, m) (1 day, m ) (2 days, m) (20It 0 days 2C12) J=9.0Hz 〉 7.09 (20,d, J=9.0H2)
Example 2 A compound represented by the following chemical formula as a raw material phenol derivative 2.50 (1, n-Co + y% o days R-(-)-epichlorohydrin 4.2
5 (] and bebenzyltriethylammonilla 90912
Dissolve 20g in dimethylformamide 3mi,
24% by weight aqueous sodium hydroxide solution (1.2 eq.) was added dropwise. 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 8 glycidyl ethers represented by the following chemical formula.

mp 90'C [α1 sweet + 4.44° (C=1.01.C eyes 2C1
2) NMR (CDα3) δ: 0.50 to 3.00 3.10 to 3.50 3.80 to 4.30 6.75 to 7,60 Example 3 Compound 10 shown by the following chemical formula as a raw material phenol derivative .0(], n-Go+roloH Same R-(-)-epichlorohydrin as in Example 1 18.
6 (1, 367 m () of piperidine) and 1 d of dimethylformamide were mixed and stirred at 60'C for 10 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and acetone 5- was added, and the mixture was stirred at room temperature for 24 hours. A wt% aqueous sodium hydroxide solution (1.2 equivalents) was added dropwise and reacted 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 removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain 8 glycidyl ethers represented by the following chemical formula: 1.
58g was obtained.

(191-1, m) (1st 1.m) (2nd, m) (8th, m) mp 131°C [α] V +3.03° (C=0.55.0 mouth 2α
2>NMR (CDα3) δ: 0.70-2.20 (170, m) 2.55-
3.00 (20, m) 3.15-3.45 (10, m) 3.75-4.20 (20, m) 6.89 (20, d, J-9,0H2)
6.92 (20,d, J=8.4Hz
)7.43 (4th stitch, d, J=9.0H
7) Example 4 5.28 g of a compound represented by the following chemical formula as a raw material phenol derivative, 11.55 g of (S)-(10)-epichlorohydrin
, 3.00 g of potassium t-nibutoxide, 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 5.82 g of R-glycidyl ether represented by the following chemical formula.

[α] l −5,71° (C=1°66.0 mouth 2α
2) NMR (CDα3) δ: 0.60-2.50 (170, m) 2.60-
2.95 (2 days, m) 3.15-3.60 (10, m) 3.80-4.30 (2 days, m) 6.76 (20, d, J=8.4H2)
7.07 (2 days, d, J=8.4H
z) Example 5 An R-form glycidyl ether represented by the following chemical formula was obtained in the same manner as in Example 4 except that the compound n-C represented by the following chemical formula was used as the raw material phenol derivative.

mp 91℃ [α] l −3,59° (C=1.07.0 mouth 2α
2) NMR (CDα3> δ: 0.85-2.93 (270, m) 3.34-
3.40 (1 to 1. m> 3.97 to 4.27 (20, m> 6.94 to 7.53 (80, m) Example 6 A compound iog represented by the following chemical formula as a raw material phenol sterilizing conductor, R-(-)-epichlorohydrin 16 as in Example 1,
07(], 220% by weight aqueous sodium hydroxide solution 733
() and 220 m of didimethylformabi at 60 m
The mixture was heated and stirred at ~70°C for 1 hour. After cooling the reaction solution, water was added and the product was extracted with dichloromethane to obtain crude product 11.67 ().The crude product was purified by silica gel column chromatography to obtain 8 products represented by the following chemical formula. Glycidyl ether 9.07 (] was obtained.

mp 74°C [α] Sweet 1.66° (C=1.02°NMR (CD
C13) δ:0.5~2,2 2.6~3.0 3.1~3.7 3.8~4,4 6.95 8.26 8.36 (t5H,m> (20,m > (IH, m> (4H, m> (2H, d, J = 9.0th Z) (20, d, J = 9.0Hz) (20, S) 0 mouth 2C12) Example 7 Raw material phenol derivative Compound 7.44 represented by the following chemical formula obtained in Production Example 1 of the phenol derivative as
(], R-(-)-epichlorohydrin 9.1 as in Example 1
6 (1.74 g of 1,50% by weight aqueous sodium hydroxide solution
and 77 tnl of dimethylformamide.
Stirred at 70°C for 3 hours. After cooling the reaction solution, add water and
The product was extracted with dichloromethane, and the extract was purified by silica gel column chromatography to obtain 8 glycidyl ethers 6,90 (] represented by the following chemical formula).

mp 198°C [α]v+0.95° (C=1.04.0 mouth 2α2)
NMR (CDα3) δ: 0.6-2.1 2.6-3.0 3.2-3.5 3.8-4.5 6.99 7.50 8.40 8.90 Example 8 Raw material 1.01g of a compound represented by the following chemical formula as a phenol derivative, (150,m) (20,m) (10,m) (20,m) (4H,d, J=9.0)12) (20,d , J=9.OH7) (20,d, J=9.0Hz) (2nd, S) Same R-(-)-epichlorohydrin 2.0 as in Example 1
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 residue obtained by distilling off the solvent under reduced pressure was recrystallized from hexane to obtain 380 mg of 8 glycidyl ethers represented by the following chemical formula.

mp 65℃ [α] tube +1.90° (C = 0.46.0 mouth 2α2) N
MR (CDC13) δ: 0.6-3°O (190, m) 3.2-3.6 (1 day, m > 3.9-4.5 (20, m) 6.99 (2H, d , J=9.0H2)8
．． 36 (2nd, d, J=9.0H2)
8.55 (20,S) Example 9 Compound 3.12(] shown by the following chemical formula as a raw material phenol derivative, R-(-)-epichlorohydrin 4.6 as in Example 1
27 (II, 50% by weight aqueous sodium hydroxide solution 0.
A mixture of sag and dimethylformamide 307
The mixture was heated and stirred at ℃ 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 2.96q of 8 glycidyl ethers represented by the following chemical formula.

mp 65°C [α]￥+2.47° (C=1.02°NMR(CD
Cb) δ: 0.6~2.0 2.4~3.0 3.2~3.5 3.8~4.5 (190, m) (40, m) (IH, m> (2H, m) 0 mouth 2α2) 6.98 (20, d, J=9.OHz
)8.33 (20,d, J=9.0Hz
)8.53 (2nd day, S) Examples 10 to 11 Table 7 shows the specific optical rotations of optically active glycidyl ethers synthesized by the same method as Examples 1 to 9.

Further, the specific optical rotations of the optically active glycidyl ethers obtained in Examples 1 to 9 are also summarized in Table 7.

In Table 7, the symbols R3, n, X and * are based on the chemical formula below.

Table (Effects of the Invention) The optically active liquid crystal compound having a γ-lactone ring obtained using the optically active glycidyl ether derivative of the present invention has good stability against heat and water, and has excellent properties as a ferroelectric liquid crystal. have.

Claims (1)

[Claims] An optically active glycidyl ether derivative represented by the following general formula (B). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) (In the general formula (B), R^1 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 * sign represents an asymmetric carbon atom)