CA1331182C - Optically active glycidyl ethers suitable for use in the preparation of liquid crystalline compounds - Google Patents

Abstract

Abstract The present invention is directed to optically active glycidyl ether of the formula:

(B) wherein R1 is a group selected from the group consisting of , and ;

n and e are each independently 0 or l; R3 is an alkyl group having 1 to 15 carbon atoms; and the symbol * denotes an asymmetric carbon atom. The ethers of the present invention are suitable for use in the preparation of liquid crystalline compounds.

Description

Optically Active Glycidyl Ethers Suitable for Use in the PreParation of Liouid CrYstalline Com~ounds This application has been divided out of Canadian Patent Application Serial No. ~6,646 filed September 7, 1988.
This invention relates to novel optically active glycidyl ethers suitable for use as intermediates in the preparation of liquid crystalline compounds. The liquid crystalline compounds that can be prepared from the intermediates of the present invention have an optically active y-lactone ring and are useful as elements in display devices or as elements in opto-electronic devices. These liquid crystalline compounds include not only compounds which can exhibit the liquid crystal phase by themselves but also compounds which do not exhibit the liquid crystal phase alone but are useful as a component of liquid crystal compositions.
Liquid crystals have been widely used as a material for display devices, where a TN (Twisted Nematic) type display system is usually employed. Advantages of such a TN display system include less electric consumption, less eye fatigue because it is a receptor type, and the like. On the other hand, disadvantages of this system include a driving force that is very weak because it is driven mainly on the basis of anisotropy of dielectric constant and slow response speed. Hence, this system cannot be applied to devices which require a high response speed.

'T~' , ~

.. . ~ ..... . , . ~ , ,~
. ,.

1331~82 - ~

Liquid crystals having ferroelectricity were first discovered by R.B. Meyer et al. in 1975 (cf. J. Physique, 36, L-69, 1975). This type of l;quid crystal is driven by a -~
comparatively large force derived from spontaneous polarization, shows extremely high response speed and also has, good memory. Because of these excellent properties, the ferroelectric liquid crystal has been noted as a new type of display element. In order to exhibit the ferro-electricity, the liquid crystalline compounds should show a chiral smectic C phase (SmC* phase) and thus should contain at least one asymmetric carbon atom in the molecule. It is also necessary to have a dipole moment in the direction vertical to the long axis of the molecule.
A ferroelectric liquid crystal DOBAM8C synthesized by Meyer et al. has the following formula~

C10H21o ~ CHIN ~ CH-CH-CO2CH2-~H-CH2CH3 and satisfies the above conditions, but it contains a Schiff base and hence is chemically unstable and showsa low ; -~
spontaneous polarization as low as 3 x 10 9 C/cm2. Since then, many ferroelectric liquid crystalline compounds have been synthesized, but practically useful compounds having sufficiently high response speeds have never been found.

Among the known ferroelectric liquid crystalline compounds, DOBA-1-MBC which ha~ the asymmetric carbon atom at the position nearer to the carbonyl group than in DO~AMBC
and has the following formula:

C1 OH21 0~cH=N~cH=cH-co2~H-c3H7 shows a spontaneous polarization of 5 x 10 8 C/cm2 which is larger than that of DOBAMBC. It is assumed that this is caused by the following difference. The asymmetric carbon atoms and the dipole which are important :
factors for the appearance of ferroelectricity are positioned close each other, and thereby, the free rotation of the dipole moiety of the molecule is depressed and the orientation of the dipole i9 increased. Thus, it is assumed that the known ferroelectric liquid crystalline compounds . .
cannot give satisfactory spontaneous polarization and high response speed because the asymmetic carbon atom having an inhibitory action of the free rotation of the molecule is .r~
present on the linear chain in the known ferroelectric liquid crystalline compounds and hence the free rotation of the molecule cannot be completely inhibited and the dipole moiety cannot be fixed.
Under the circumstances, the present inventors have studied intensively in an effort to determine a method of inhibiting the free rotation of the dipole moiety in conventional ferroelectric liquid crystalline compounds and - ~3~11=82 have found that the free rotation can be inhibited by providing a compound wherein the asymmetric carbon atom is contained in a 5-membered lactone ring, by which there can be obtained a chemically stable-liquid crystalline compound having ferroelectricity.
The present invention thus provides in one embodiment an optically active glycidyl ether of the formula~

R -O ~ (B) O ' wherein Rl is a group selected from the group consisting of R3~(0)n ~ ~ R3~(0)n ~ and R3-()n ~ N

n and e are each independently O or l; R3 is an alkyl group having 1 to 15 carbon atoms; and the symbol * denotes an asymmetric carbon atom, which can be used to prepare liquid crystalline compounds of the formula (A) as set out below.
In drawings which illustrate preferred embodiments of the present invention as well as the invention set out in the parent application:
Fig. 1 shows a graph of the relationship between the relative dielectric constant and temperature in the q-lactone derivative prepared in Example l.

- 4a -Fig. 2 shows a graph of the relationship between the relative dielectric constant and temperature in the y-lactone derivative (2S, 4S) prepared in Example 32.
The liquid crystalli;~-compounds prepared using the novel optically active glycidyl ethers of the 1331~8~
. 5 invention are compounds having an optically active q-lactone ring and having the following formula~

R 1 _ 0~ R2 I ¦ (A) ~0 ,.

wherein R1 is a group selected from the group consisting of R3~(0)n ~ ~ R3~(0)n ~ , and R3~(0)n ~ \ ~ , n and e are each independently O or 1, R3 is an alkyl group having 1 to 15 carbon atoms, R2 is a group of -(Co)m-R4, m is O or 1, and R4 is a hydrogen ~:
atom or an alkyl group having 1 to 15 carbon atoms, and * ~

denotes an asymmetric carbon atom. ~.
In the specification, the term "alkyl group" for R3 :
and R4 includes 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-methyl-is hexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methyl-heptyl, 2-methylheptyl, 1-methylheptyl, 7-methyloctyl, 6-methyloctyl, 5-methyloctyl, 4-methyloctyl, 3-methyloctyl, 2-methyloctyl, 1-methyloctyl, 8-methylnonyl, 7-methylnonyl, 6-methylnonyl, 5-methylnonyl, 4-methylnonyl, 3-methylnonY1, 2-I methylnonyl, 1-methylnonyl, 3,7-dimethyloctyl, 3,7,11-¦ trimethyldodecyl, and the like.
The compounds of the parent application contain a carbonyl group within a 5-membered ring and one or two -asymmetric carbon atoms on the ring as a moiety having a dipole moment as an origin of ferroelectricity, and hence, the free rotation at this moiety is inhibited and thereby the dipole moiety is directed to one direction, which is effective for enlarging the spontaneous polarization and for increa~ing the response speed. In the liquid crystalline compounds (A) of this invention, when R2 is a hydrogen atom, only one asymmetric carbon atom i5 contained, but when R2 is a group other than hydrogen, two asymmetric carbon atoms are lS contained in the ~-lactone ring and hence there are present two kinds of diastereomer. These are all suitable for inhibition of free rotation of the dipole moiety, and they are used as a liquid crystal alone or in a mixture of two or more thereof.
The compounds of the formula (A) can be prepared by a process which comprises reacting an optically active glycidyl ether of the formula:
R1_o ~ (B) :, -:
wherein R1 and the symbol * are the same as R1 and * in the -;
formula (A), with a ~-ketoester or malonate of the formula, respectively 1 3 3 1 1 8 2 ~ ~
,~`` ~`, o o . . :. ~ .
R4 ~ oR5 ~- (C) ~ ~ -~
: ~ ....
or O O .
~:.
R50 ~ oR5 (D) wherein R4 is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms and R5 is a lower alkyl group having 1 to 4 carbon atoms, in the presence of a base in an organic solvent.
The starting optically active glycidyl ether (8) can be prepared by a process a~ shown in the following reaction scheme:

* ~
~ Cl R10H - ~ Rl-Base o wherein Rl and the symbol * are the same as R1 and * in the formula (A).

That is, a phenol derivative of the formula R1OH is reacted with an optically active epichlorohydrin in the . .. -pre~ence of a base. The optically active epichlorohydrin is ;~
preferably used ln an amount of 1 to 10 equivalents to 1 equiv~
alent of the phenol derivative, and the base is preferably :" - 81-331182 used in an amount of 1 to 5 equivalents to 1 equivalent of the phenol derivative. The base includes alkali metal hydroxides or alkoxides, e.g. sodium hydroxide, potassium hydroxide, potassium t-butoxide~,-and the like. The above -reaction may procee~ smoot~ly ~7ithouta catalyst, but may be carried out in the presence of a catalyst. The catalYst may include quaternary ammonium halides, e.g. benzyltri-ethyl ammonium chloride, benzyltriethylammonium bromide, henzyltrimethylammonium chloride, benzyltrimethylammonium bromide, etc. and is used in an amount of 0.01 to 0.1 equivalents to l equivalent of the phenol derivative. An excess amount of the optically active epichlorohydrin m~y be used as the solvent, but there is preferably used a suitable polar solvent, e.g. dimethylformamide, dimethyl-sulfoxide, dimethylacetamide, acetonitrile, t-butyl alcohol, and water. The reaction is usually carried out at a temperature of 50 to 80 C for 0.5 to 3 hours.
Alternatively, the optically active glycidyl ether tB) mav also be prepared by reacting the phenol derivative of the formula RlOH with an optically active epichlorohydrin in the presence of an amine (e.q.
morpholine, piperidine, pyridine, etc.) of O.l to 0.5 equivalents to 1 equivalent of the phenol derivative and -~
subjecting the resulting optically active chlorohydrin derivative to a cyclization reaction with l to 5 equiva-lents of a base, for example, an alkali metal hydro~ide, ; ~ ~
':

13311~2 .~
carbonate or alkoxide (e.g. sodlum hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium t-butoxide, etc.). The latter process is carried out in two steps but is advantageous in that the extraction of the product can easily be done. This reaction is usually carried out at a temperature of 50 to 80C for 3 to 24 ;
hours.
When a racemic epichlorohydrin is used in the above reaction, there is obtained a glycidyl ether in the form of a racemic mixture. The starting optically active epichloro-hydrin can be prepared in a high purity by the processes as described in-Japanese Patent First Publication (Kokai) Nos.
132196/1986 and 6697/1987 (as to R isomer) and by the process as described in Japanese Patent Application No.
283393/1987 (as to S isomer).
The starting phenol derivative used for the preparation of the compound (B) can be prepared by the processes as shown in the following Reaction Schemes I to VI, wherein R3 is the same as R3 in the formula (A), R3 is a hydrogen atom or an alkyl group having a carbon atom one ;
smaller than that in R3, Ph means phenyl, and R' is a lower alkyl group having 1 to 4 carbon atoms.
That is, 4-(4-trans-alkylcyclohexyl)phenols, 4-(4-alkyloxyphenyl)phenols, and 4-(4-alkylphenyl)phenols are prepared by the known processes as shown in Reaction Schemes I, II and III, respectively.

., _ ....... . . . . .

Reaction Scheme-I

R3 CO ~ Cl Q R3 CO

,l~ NH2N~2 H20 R3'C~2 ~

AlCl3 ~ CH3COCl R3 CH2 ~ 1) H202; ~C02H 3~ ~ COCH3 2) H30 Reaction Scheme-II
.

C~I3C02~ ~ CH3Co2~3CocH3 ~ ~30~ ~ ;

HO ~ COC~3 -- ;
~ R3X
R30-~3oE~ 1<) H202 ~ EIC02H R30~ COCH3 2) H30 Reaction Scheme-III -~

CH3C02 ~ AlCl3 CoR3 ~ NH2NH2-H20 HO ~ CH2~3 ~:~

. 4-(5-Alkyl-2-pyrimidinyl) phenols and 4-(5-alkyloxy-2-pyrimidinyl)phenols are prepared by the processes 13311~2 as shown in the followin~ Reaction Schemes IV and V, respectively, which are disclosed in Japanese Patent First :~ .
Publication (Kokai) Nos. 189274/1986 published Au ~ t 22, 1986.
Reaction Scheme-IV
(CH3)2NCHO 3 /~caN(CH3)2 R CH2CH(OC2H5)2 > R C
POC13 \C~O
--~1) C2H5~H, HCl fi--~ /NH
HO~ CN ~ HO~ C/ HCl- ~
2) NH3~=~ ~NH2 ~ NaOC2~5 / R3 ~ ~ ~ OH
/ N
H2 r Pd-C
C~Y)~}~

NaOC2Hs P~3CH(co2c2H5~2 ~ 3~ N\~ / POC13 ~ N ~ OH
o// H ~: :

Reaction Scheme-V -~
. .
R3~H + BrcH2cH~oc2H5)2 ~ R3ocH2cH(oc2Hs)2 ~ (CH3)2NCHO - POC13 :~-Ho~3~/NH E~Cl N~ \NH2 :3 ~CHN(CH3)2 R30~ OH-C R O ~
\=N~ NaOC2H5 CHO

. Moreover, 4-[5-(4-alkyloxyphenyl~-2-pyrimidinyl]- :
25phenols and 4-[5-(4-alkylphenyl)-2-pyrimidinyl]phenols are ~ . ., ,.,,.. . .... ~.. ~ ...... . . . - .

prepared by the processes as shown in the following Reaction Scheme-VI.
Reaction Scheme-VI

HO ~ CN HO ~ CH2CO2H R3 ~ COCE3 ~ PhCH2Cl R'OH ~ H+ S ~ ~ ~

PhCH2O ~ CNHO ~ CH2CO2R' R ~ CH2CO2H

l) C2H5OH, HCl R3X ~ ~ R'OH, H+
2) NH3 ~NH R3O ~ CH2C2R' R3 ~ CH2CO2R' PhCH2O ~ C ~Cl :~
~=~ ~NH2 ~ / ,OR' -~-~
(E) \ / O=C :~

Rt ~ CH(cO2R )2 NaOC2H5 . -I (F) n = 0 ~ ::
\ f ~G) n = l .

R3-~o ~ \ ~ OCH2Ph . O H ~ POCl3Cl R3t O ~ ~ ~ OCH2Ph H2 ~ Pd-C

R3t O ~ \ ~ OH

(H) n = 0 - :
(I) n = l ~ - 13 13311~2 According to the process of Reaction Scheme-VI, Compound (E) is prepared by protecting the hydroxy group of p-hydroxybenzonitrile with a benzyl group and converting the cyano group thereof into an amidine hydrochloride in a usual manner. Separately, p-hydroxyphenylacetic acid is esteri-fied with a lower alcohol, and the pnenolic hydroxy group is alkylated with an alkyl halide, alkyl p-toluenesulfonate or alkyl methanesulfonate, followed by reaction with diethyl carbonate in the presence of a base to give a diethyl malonate ~;
. .
derivative (G).
The amidine hydrochloride (E) is condensed with the diethyl malonate derivative (G) in the presence of a base, for example~alkali metal alkoxides (e.g. sodium ethoxide, sodium methoxide, etc.), followed by reaction with phosphorus oxychloride in the presence of a base, for example, organic amines (e.g. N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)-pyridine, etc.), and the resulting compound is reduced with hydrogen gas in the presence of Pd-C catalyst to give the de~ired 4-[5-(4-alkyloxyphenyl)-2-pyrimidinyl]phenol (I). -In the above process, when a diethyl p-alkylphenyl-malonate (F) i9 used instead of the diethyl malonate derivative (G) and the compound (E) and the compound (F) are reacted as in the reaction of the compound (E) and the compound (G), there is prepared 4-~5-(4-alkylphenyl)-2-pyrimidinyl]phenol (H).
The diethyl p-alkylphenylmalonate (F) can be . ' . . ~ ' . ' ' ' ' ' prepared by subjecting a p-alkylacetophenone to a Willgerodt reaction, esterifying the resulting phenylacetic acid derivative with a lower alcohol, and condensing the resultant product with diethyl carbonate.
The desired compound (A) of this invention can be prepared by reacting under reflux the compound (~) with 1 to ;~
5 equivalents of the compound (C) or the compound (D) in the presence of 1 to 5 equivalents of a base in an organic solvent for 1.5 to 24 hours. The base used therein includes ~ -~
alkali metal alkoxides (e.g. sodium methoxide, sodium ethoxide, potassium t-butoxide, etc.), alkali metal hydrides (e.s. sodium hydride, lithium hydride, etc.), and alkyl alkali metals (e.g. n-butyllithium, etc.), and the organic solvent includes alcohols (e.g. methanol, ethanol, t-butyl alcohol, etc.), ethers (e.g. tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, dioxane, etc.), aprotic polar solvents (e.g. dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, etc-.), and a mixture of these solvents.
In the above process, when R4 in the compound (D) is a hydrogen atom, the final compound prepared by the process is mixed with an inorganic salt (1 to 10 equivalents) and water under neutral condition and then is refluxed in a polar solvent to give the desired compound (A). The solvent u~ed therein includes polar solvents, e.g.
dimeth~lformamide, dimethylacetamide, dimethylsulfoxide, ;. -, . . . , , ~. ,~ i : .. ... ~ . ~ , : ~ -: . . :,:..... : : .: :: , .. . .. : : :

~31~82 hexamethylphosphoric triamide, diethylene glycol dimethyl ether, dioxane, and the like. The inorganic salt includes alkali metal or alkaline earth metal halides, e.g. lithium chloride, sodium chloride, pot~ssium chloride, lithium 5 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. Water is preferably used in an amount of 5 to 50 equivalents. The reaction is completed in 1 to 15 hours.
The liquid crystalline compounds prepared using the optically active glycidyl ethers of this invention may be obtained in the form of a racemic mixture when a racemic epichlorohydrin is used as the starting material, and the racemic compounds may be added to other optically active liquid crystalline compounds in order to regulate the helical pitch thereof. The liquid crystalline compounds have excellent heat stability and light stability, and the optically active compounds have excellent properties as ferroelectric liquid crystals. The liquid crystalline compounds are also useful for the following utilities.
(1) Additives for TN (Twisted Nematic) type or STN (Super Twisted Nematic) type liquid crystals in order to inhibit occurrent of reverse domain.
(2) Display element utilizing cholesteric nematic phase transfer effects (cf. J.J. Wysoki, A. Adams and W. Haas; Phys. Rev. Lett., 20, 1024, 1968).

` 1331182 (3) Display element utilizing White-Taylor type guest host effects (cf. D.L. White and G.N. Taylor; J. Appl.

Phys., 45, 4718, 1974).

(4) Notch filter or band-pass filter utilizing -.~ - .

5 selective scattering effects by fixing the cholesteric phase ~-in matrix (cf. F.J. Kahn; Appl. Phys. Lett., 18, 231, 1971).
(5) Circularly polarized light beam splitter ~ ~
utilizing circularly polarized light characteristics of the -cholesteric phase (cf. S.D. Jacob; SPIE. 37, 98, 1981).
This invention set out in the present application as well as that set out in the parent application is illustrated by the following Preparations and Examples, but should not be construed to be limited thereto.
In the Examples, the positions of R and S in the optically active compounds (A) are shown by the position numbers in the following formula: ~
: ' R1 -0--~R2 O ~ (A) ,' ' The phase transfer temperature in the Examples was measured by DSC (Differential Scanning Colorimetry) and with a polarizing microscope. The symbols in the phase transfer 20 temperature mean as follows: v C : Crystalline phase SmA: Smectic A phase SmC: Smectic C phase ','''''~

1 3 3 1 1 ~ 2 :~"
SmC*: Chiral smectic C phase Sml: Non-identified ~mectic phase other than SmA, SmC and SmC*.
N: Nematic phase - ;`
N*: Chiral nematic phase I: Isotropic liquid The chiral smectic C phase (SmC*) was further confirmed by measuring the dielectric constant thereof.
Preparation o~ phenol derivatives Preparation 1 Preparation of 4-[5-(4-n-octyloxyphenyl)-2 pyrimidinyl]phenol~
i) Preparation of 4-benzyloxyphenylamidine hydro-chlor~de.
4-Cyanophenol (95.2 g), benzyl chloride (127 g) and potassium carbonate (138 g) were refluxed in acetone (160 ml for 5 hours. The product was separated by filtration, concentrated under reduced pressure, and ~
; benzene thereto was added. The mixture was washed wit'n `
water, and benzene was distilled off under reduced pressure to give 4-benzYloxybenzonitrile (141.38 g). The , . . .
4-benzyloxvbenzonitrile (141 g) was dissolved in benzene (338 ml), ethanol (270 ml) was added thereto and the - -mixture was cooled to 0C. Into the resulting slurry was bubbled hydrogen chloride gas (36 liters) with -13311~2 : ~
stirring. Thereafter, the temperature was raised to 25C, arld the mixture was allowed to stand for 2 days. The reaction mixture was concentrated under reduced pressure to a 1/3 volume, and ether was added to ~he concentrated mixture . The precipitated crystals were separated by suction filtration to give an imide ester (183 g).
The above-obtained imide ester (183 g) was mixed with ethanol (270 ml) to give a slurry, and a solution of ammonia ;~
(60.75 g) in ethanol (405 ml) was added thereto. After allowing the mixture to stand at room temperature for 2 days, the solvent was distilled off under reduced pressure to give 4-benzyloxyphenYlamidine h~drochloride (154.5 g). NMR
(DMSO-d6) ~: 5.19 (2H, s), 7.17 (2H, d, J=9.0 Hz), 7.35 (5H, ~
s) 7.86 (2H, d) ~ -ii) Preparation of diethyl 4-n-octyloxyphenyl-malonate:
4-Hydroxyphenylacetic acid (50.0 g) was dissolved in ethanol (400 ml) and conc. sulfuric acid (0.5 ml) was added thereto. The mixure was refluxed with stirring, and ethanol was distilled off to give ethyl 4-hydroxyphenylacetate (60 g).
The ethyl 4-hydroxyphenylacetate (59 g) and sodium ethoxide (22.4 g) were dissolved in ethanol (150 ml) and n-octyl bromide (63.5 g) was added. The mixture was refluxed for 3 ho~3rs, concentral:ed under reduced pressure, and ethYl acetate was added there to to dissolve the oily - 19 - ~: ' substance. The mixture was washed with water, dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove ethyl acetate, and further distilled ;
under reduced pressure to give~ethyl -4-n-octyloxyphenylacetate (79.6 g, b.p. 179C/0.1 mmHg).
The obtained ethyl 4-n-octyloxyphenylacetate (79 g), ethanol (140 ml), diethyl carbonate (300 ml) and sodium ethoxide (19.3 g) were mixed, and the mixture was heated with stirring while ethanol was distilled off. The reaction 10 mixture was transferred into ice water and acidified with hYdrochloric acid. The organic layer was separated and the solvent distilled off to give diethyl 4-n-octyloxvphenYlmalonate (91.6 g).
NMR (~DC13) ~: 0.5-2.0 (21H, m), 3.90 (2H, t, J=~.0 Hz), ~.16 (4H, a, J=7.2 Hz), a.52 (lH, s), 6.80 (2H, d, J=9.0 H~), 7.26 (2H, d, J=9.0 Hz) ~- -iii) Preparation of 4-[5-(4-n-octyloxyphenyl)-2-pyrimidinyl]phenol:
4-Benzyloxyphenylamidine hydrochloride (65.6 g) and diethyl 4-n-octyloxyphenylmalonate (91.0 g) were dissolved in methanol (500 ml) and thereto was added sodium methoxide (44.8 g). The mixture was refluxed with stirring for 9 hours.
After cooling, the reaction mixture was acidified with sulfuric acid, and the precipitated crystals were separated by suction filtration to give yellow crystals (77.7 g).
The ahove yellow crystals (77 g), phosphorus oxy-chloride (310 ml) and N,N-diethvlaniline (4~.5 ml) were mixed ,.. ,.",., .,., .. ~., . - -.. -~

7 :

~ 1331182 :~

and refluxed with stirring for 26 hours. The excess phosphorus oxychloride was d stilled off under reduced pressure, the residue transferred into ice-water and extracted with ether. The extract was washed with water and distilled to remove ether to giv~ a crude product (70 g).

The product was recrystallized from ether to give a compound (21 g) of the following ~ormula:

n-C8H1 70~N>~-OCH2Ph ' (Ph: phenyl) NMR (CDC13) ~: 0.4-2.1 (15H, m), 3.99 (2H, t, J=6.o Hz), 5.09 (2H, s), 6.7-7.5 (11H, m), 8.38 (2H, d, J-9.0 Hz) The colorless crystals obtained above (19.8 g), ethanol (757 ml), magnesium oxide (11.4 g), water (57 ml) and 10 ~ Pd-C (4 g)were heated with stirring at 60OC under hydrogen atmosphere until a theoretical amount of hydrogen was absorbed. The reaction mixture was filtered with suction, and the filtrate was concentrated to give the desired 4-~5-(4-n-octyloxyphenyl)-2-pyrimidinyl]phenol (7.7 g), m.p.

137C.

NMR (CDC13) ~: 0.5-2.1 (15H, m), 4.00 (2H, t, J-6.o Hz), 6.92 (2H, d, J-9.0 Hz), 7.01 (2H, d, JD9.0 Hz), 7.50 (2H, d, J~9.0 Hz), 8.30 (2H, d, J-9.0 Hz), 8.94 (2H, s) ~Preparation o~ the compounds (B)]:

The starting optically active epichlorohydrins were prepared by the processes as disclosed in Japanese Patent ~-: ~

1331182 - ~

First Publication (Kokai) Nos. 132196/1986 and 6697/1987 and in Japanese Patent Application No. 283393/1987. These were R-(-)- and S-(l)-epichlorohydrins which have a chemical purity of 98.5 % or more (measured by gas chromatographic analysis) and an optical purity of 99 % or more [the specific rotation, [a]D = -34.0, +34.0, c = 1.2, methanol, respectively].
Preparation 2 To a mixture of the above R-(-)-epichlorohydrin ~;
(5.55 g), 4-(trans-4-n-pentylcyclohexyl)phenol (2.46 g) of the following formula:
n C5H~1 ~ OH
and benzyltriethylammonium chloride (0.04 g) was added dropwise aqueous sodium hydroxide (NaOH 0.45 g, water 15 ml) with stirring at 600C over a period of 20 minutes, and the mixture was further refluxed for one hour. The reaction mixture was cooled to room temperature and extracted twice with ether. The extract was washed once with a saturated saline solution and distilled under reduced pressure to remove the solvent. The residue was purified by silica gel chromatography to give (S)-2,3-epoxypropyl 4-(trans-4-n-pentylcyclohexyl)phenyl ether (1.8 g) of the following formula:

n C5H11 ~

13311~2 [a]2D5- +4.44 (c - 1.36, CH2Cl2) NMR (CDC13) ~: 0.45-2.50 (21~- m), 2.50-3.00 (2H, m), 3.15- -3.50 (1H, m), 3.70-4.30 (2H, m), 6.79 (2H, d, J=9.0 Hz), 7.09 (2H, d, J=9.0 Hz) Preparation 3 ~ The starting phenol derivative (2.50 g) of the ¦ following formula:
n-CgH17~0H
and the same R-(-)-epichlorohydrin (4.25 g) and benzyl-10 triethylammonium chloride (20 mg) as used in Preparation 2 were dissolved in dimethylformamide (3 ml) and thereto was added dropwise 24 wt.~ aqueous sodLum hydroxide t1.2 equi-valent) at 60oC. After reacting at the same temperature for 40 minutes, the reaction mixture was cooled to room 15 temperature and extracted with ether. The extract was distilled under reduced pressure to remove the solvent. The residue was p~rified by silica gel chromatograrhy to give an S
isomer of glycidyl ether (1.62 g) of the following formula:

n-CgH17 ~
m.p. 90C
[]D5- ~4 44 (C ~ 1.01, CH2Cl2) NMR (CDCl3) ~: 0.50-3.00 (19H, m), 3.10-3.50 (1H, m), 3.80- -~
4.30 (2H, m), 6.75-7.60 (8H, m) :~?. ~
~ .-. . . : ~ ~ : :.:. :,: - : ~ .

1331182 ~

Preparation 4 The qtarting phenol derivative (10.0 g) of the following formula:
n-C8H170~0H
and the same R-(-)-epichlorohydrin (18.6 g) as used in Preparation 2, piperidine (367 ml) and dimethylformamide (1 ml)were mixed and stirred at 60OC for 10 hours. The reaction mixture was distilled under reduced pressure to remove the solvent and acetone ~5 ml) was added thereto.
Further, a 24 wt.~ aqueous sodium hydroxide (1.2 equivalent) was added dropwise with stirring at room temperature, and the mixture was reacted for 30 minutes. The reaction mixture was adjusted to pH 7 with 2N hydrochloric acid and extracted with ethyl acetate. The extract ~Tas dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The residue was purified by silica gel chromatography to give S isomer of glycidyl ether (1.58 g) of the following formula~

n-CgH170~0/?~7 m.p. 131C
~]D ~ +3-3 (c - 0.55, CH2C12) NMR (CDC13) ~: 0.70-2.20 (17H, m), 2.55-3.00 (2H, m), 3.15-3.45 (lH, m), 3.75-4.20 (2H, m), 6.89 (2H, d, J~9.0 Hz), 6.92 (2H, d, J~8.4 Hz), 7.43 (4H, d, J-9.0 Hz) -,. ~

13311~2 Preparation 5 A phenol derivative (5.28 g) of the following formula:
n C3H7 O~OH~
S-(I)-epichlorohydrin (11.55 g), potassium t-butoxide (3.00 g) and t-butyl alcohol (45 ml) were mixed and the mixture stirred at 600C for 3 hours. The reaction mixture was distilled under reduced pressure to remove the solvent and ~ ~
the residue extracted with chloroform. The extract was ~-distilled under reduced pressure to remove the solvent. The residue ~7as purified by silica gel chromatography to give R
isomer of glycidyl ether (5.82 g) of the following formula:

n-c3H7 0~ /~

[~]3D ~ ~5-71 (c ~ 1.66, CH2Cl2) NMR (CDCl3) ~: 0.60-2.50 (17H, m), 2.60-2.95 (2H, m), 3.15-3.60 (1H, m), 3.80-4.30 (2H, m), 6.76 (2H, d, Js8.4 Hz), 7.07 (2H, d, J~8.4 Hz) Preparation 6 In the same manner as described in Preparation 5 except that a compound of the following formula: -~ ~ -n-C1 2H25~0H
was used as the starting phenol derivative, there was prepared ~ ~
R i~omer of glycidyl ether of the following formula: ~-n-C12H25~ ~7 m.p. 91C
[a]D ~ ~3-59 (c 3 1.07, CH2Cl2) NMR (CDCl3) ~: 0.85-2.93 (27H, m), 3.34-3.40 (1H, m), 3.97-4.27 (2H, m), 6.94-7.53 (8H, m) Preparation 7 A mixture of the starting pnenol derivative (10 g) of the following formula:

n-C8H17 ~ \ ~ OH, the same R-(-)-epichlorohydrin (16.07 g) as used in Preparation 2, 20 wt.% aqueous sodium hydroxide (7.33 g) and dimethylformamide (20 ml) was heated with stirring at 60-70C
for one hour. The reaction mixture was cooled and thereto was added water. The mixture was extracted with chloroform to obtain a crude product (11.67 g). The crude product was purified by silica gel chromatography to give an S isomer of glycidyl ether (9.07 g) of the following formula:

n-C8H170 ~ N ~ O

m.p. 74C -~-~a]D ~ +1.660 (c 3 1.02, CH2Cl2) NMR (CDCl3) ~: 0.5-2.2 (15H, m), 2.6-3.0 (2H, m), 3.1-3.7 (1H, m), 3.8-4.4 (4H, m), 6.95 (2H, d, J=9.0 Hz), 8.26 (2H, ~ r d, J-9.0 Hz), 8.36 (2H, s) Preparation 8 A mixture of the starting phenol derivative (7.44 g) of the following formula:

~ ,.. .. . ... .. . .. ;.~ . . . .. . . . . . . . .

` - 25 - ~ ~

n-CgH170 ~ N ~ OH

as prepared in Preparation 1, the same R-(-)-epichlorohydrin (9.16 g) as used in Preparation 2, 50 wt.% aqueous sodium hydroxide (1.74 g) and dimethylformamide (77 ml) was stirred at 60-700C for 3 hours. The reaction mixture was cooled and wa~er was added. The mixture was extracted with dichloromethane. The extracted product was purified by silica gel chromatography to give an S isomer of glycidyl ether (6.90 g) of the following formula:

n-CgH1 70~N>~ ~7 m.p. 198C ;~
~a]D ~ +0.95 (c = 1.04, CH2Cl2) NMR (CDC13) ~: 0.6-2.1 (15H, m), 2.6-3.0 (2H, m), 3.2-3.5 (lH, m), 3.8-4.5 (2H, m), 6.99 (4H, d, J-9.0 Hz), 7.50 (2H, d, J-9.0 Hz), 8.40 (2H, d, J-9.0 Hz), 8.90 (2H, s) -~;
Preparation 9 The starting phenol derivative (1.01 g) of the following formula:

n-CgH17 ~ N ~ OH, the same R-(-)-epichlorohydrin (2.01 g) as used in Preparation 2 and benzyltriethylammonium chloride (16 mg) were mixed and heated at 70C, and a 24 wt.% aqueous sodium hydroxide (650 mg)was dropwise added thereto. The mixture was stirred at 70C for 2 hours. The reaction mixture was cooled ~ ~ - 27 to room temperature and extracted three times with chloroform. The.extract was dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent. The residue was recrystallized from hexane to give an S isomer of glycLdyl ether (380 mg) of the following formula:

n-c8H17 ~ N

¦ m-p- 65C
1 10 ~]D = ~1.90 (c = 0.46, CH2C12) NMR (CDCl3) C: 0.6-3.0 (19H, m), 3.2-3.6 (lH, m), 3.9-4.5 (2H, m), 6.99 (2H, d, J~9.0 Hz), 8.36 (2H, d, J-9.0 Hz), 8.55 (2H, s) Preparation 10 -. :
A mixture of the starting phenol derivative (3.12 g) of the following formula:

n-C10H21 ~ \ ~ OH, the same R-(-)-epichlorohydrin (4.627 g) as used in Preparation 2, 50 wt.% aqueous sodium hydroxide (0.88 g) and dimethylformamide (30 ml) was heated with stirring at 60C
~or 2.5 hourc. The reaction mixture was cooled and distilled under reduced pre~sure to remove the solvent. The product was purified by silica gel chromatography to give an ~ isomer of glycidyl ether (2.96 g) of the following formula:

n-C10H21 ~ N ~ ~

- 28 - ~
1331~82 m.p. 650C
[a]D7= +2.47 (c = 1.02, CH2Cl2) NMR (CDC13) ~: 0.6-2.0 (19H, m), 2.4-3.0 (4H, m), 3.2-3.5 (lH, m), 3.8-4.5 (2H, m), 6.98 (2H, d, J=9.0 Hz), 8.33 (2H, d, J=9.0 Hz), 8.53 (2H, s) Preparations 11-12 In the same manner as described in Preparations 2-10, there were prepared optically active glycidyl ethers as shown in Table 1, wherein R3, n, X and the symbol * are of the following formula:
3 ~
R ~(0)n~X~0 ~0/ ~-Table 1 ~ ,: ~:;
No. R3 n - [a]D
_ r-~ r~~~ +4.780 (c = 1.08, 11 n-C6H13 0 ~ S CH2Cl2, 30C) _ _ r~ +3.860 (c = 1.06, 12 n-CgH19 0 ~ S CH2Cl2, 31C) Preparation of Compound (A) Example 1 A dispersion of 50 wt.% sodium hydride (224 mg) in m~neral oil was washed twice with dry ether and dry tetra-hydrofuran (lO ~l) was added thereto. To the mixture was added dropwise methyl 3-oxododecanate (1.07 g) with stirring at 40OC. After stirring the mixture for 5 minutes, (S)-2,3-, , .. , ~ ~ . .... . . ... . . . . .

`~ - 29 -epoxypropyl 4-(trans-4-n-pentylcyclohexyl)phenyl ether (1.41 g) as prepared in Preparation 2 was added dropwise to the reaction mixture, and the mixture was refluxed for 20 hours. The reaCtion mixture was cooled to room temperature and 4N hydrochloric acid was dropwise added thereto until the pH was adjusted to l. The mixture was extracted twice with ether, and the extract was washed once with a saturated saline solution and distilled under reduced pressure to remove the sol-vent. The residue was purified by silica gel chromatography to give y-lactone derivatives (A) (430 m~ as a mixture of (2S,4S) isomer : (2R, 4S) isomer = 50 : 50) of the following f ormulae:
(2R, 4S) isomer:

n C5H11 ~ ~ C0-C9H19-n 1 (2S, 4S) isomer:

n~C5H11 ~ 0 ~ Co-c9H1g-n H o H

NMR (CDCl3) ~: 0.87-1.86 (39H, m), 2.26-3.06 (3H, m), 3.73-4.21 (3H, m), 4.85-4.90 (1H, m), 6.82 (2H, d, J-8.54 HZ), 7.12 (2H, d, J-8.55 Hz) IR (KBr): 1778, 1720 cm~1 ~a]D9~ +18.1 (c - 1.06, CHCl3) 25 C e~ SmC* SmA ~ - I
>

13311~2 The Y-lactone derivative~ prepared in the above Example 1 were sealed in a cell made of glass wherein a polyethylene terephthalate fiIm (thicl<ness 50 llm) was used as a spacer. The cell was charged with an alternating current of 70 Hz, and the relative dielectric constant was measured by a bridge method. The results are shown in the accompanying ~ ;~
Fig. 1. It is clear from the test results that these :
compounds have ferroelectric properties.
Example 2 In the same manner as described in Example 1 except that methyl 3-oxononanate (1.14 g) was used instead of methyl 3-oxododecanate, it was reacted with (S)-2,3-epoxypropyl 4-(trans-4-n-pentylcyclohexyl)phenyl ether as prepared in Preparation 2 to give Y-lactone derivatives (A) (970 mg, as a mixture of (2S, 4S) isomer: (2R, 4S) isomer ~ 50 : 50) of the following formulae:
(2R, 4S) isomer:
A ~j\ /y~, C~C6H13-n n-C5H11 ~ H 0- ~0 (2S, 4S) isomer:
A fi~ /~ CO-C6H1 3-n n~c5H11 V~ H 0 NMR (CDCl3) ~: 0.87-1.88 (33H, m), 2.20-3.09 (3H, m), 3.72-4.21 (3H, m), 4.77-4.99 (lH, m), 6.81 (2H, d, J-8.55 Hz), 7.10 (2H, d, J~8.55 Hz) IR (KBr): 1762, 1716 cm , . 31 - .

~]D = +13-3 (c = 1.09, CHCl3) C ~ S~C* ~ SmA

Example 3 ~ : .
A dispersion of 50 wt.~ sodiu~ hydride (224 mg) in mineral oil was washed twice with dry ether and dry tetrahydro~
furan (lO ml) was added thereto. To the suspension was ,; ,.,,...,~
added dropwise dimethyl n-butylmalonate (130 mg) with stirring at 40C. After stirring the mixture for 5 minutes, (S)-2,3-epoxypropyl 4-(trans-4-n-pentylcyclohexyl)phenyl ether (1.41 g) as prepared in Preparation 2 was added :: ,.
dropwise to the mixture, and the mixture was refluxed with stirring for 20 hours. The reaction mixture was cooled to room temperature and 4N hydrochloric acid was added dropwise thereto until the;pH was adjusted to l. The ~ixture was extracted twice with ether, and the extract was washed once with a saturated saline solution and distilled under reduced pressure.to.remove,the.solvent. The residue was purified by silica gel chromatography to give y-lactone derivatives, (2S, 4S) isomer and (2R, '4S) isomer -(50.mg. and 40 mg, respectively) of the follo~in~ 'f'ormu-lae~
(2S, 4S) isomer~
~ fi~ /~\~c4H

n C5H11 ~ ~ 0 ` ~ H

' ;~

:: ~

:

1 3 3 1 1 ~ 2 Phase transfer temperature~
C ~ I

[~]D - +33.45 (C = 0.658, CH2Cl2) NMR (CDCl3) ~: 0.88-1.98 (30H, m), 2.38-2.67 (3H, m), 4.07-4.13 (2H, m), 4.67-4.73 (1H, m), 6.83 (2H, d, J-8.3 HZ), 7.12 (2H, d, J=8.3 HZ) IR (KBr): 1762 cm~
Elementary analysis for C26H4003:
Calcd. (%): C,77.95; H,10.07 Found (%): C,77.91; H,10.12 (2R, 4S) isomer:
n-C5H11 ~ ~ C4H9-n Phase transfer temperature:
` C ~ I

[a]D ~ +20.37 ~c - 1.05, CH2Cl2) NMR (CDCl3) ~: 0.70-2.95 (33H, m), 4.00-4.25 (2H, m), 4.50-4.95 (lH, m), 6.77 (2H, d, J-8.4 HZ), 7.11 (2H, d, J-8.4 HZ) -IR (KBr): 1762 cm Example 4 Dry l,2-dimethoxyethane (3 ml) was added to a disper-sion of 50 wt.% sodium hydride (163 mg) in mineral oil, and a solution of dimethyl n-heptylmalonate (716 mg) in 1,2-dimethoxyethane (3 ml) was added thereto dropwise with stirring at room temperature over a period of 10 minutes.
A~ter stirring the mixture for 5 minutes, a solution o~ (S)-1~311~

2,3-epoxypropyl 4-ttrans-4-n-pentylcyclohexyl)phenyl ether (940 mg) as prepared in Preparation 2 in 1,2-dimethoxyethane (4 ml) was added dropwise to the mixture over a period of lO -minutes, and the mixture was refluxed with stirring for 2.5 ,~
hours. The reaction mixture was cooled to room temperature and 4N hydrochloric acid was dropwise added thereto until the pH was adjusted to l. The mixture was extracted twice with ether, and the extract was washed once with a saturated saline solution and distillsd under reduced ~ressure to remove the solvent. The residue was purified by silica gel chromatography to give a y-lactone derivative, (2S, 4S) isomer (13 mg) of the following formula:
(2S, 4S) isomer:

n-C5H1 1 0~o~/~C7H1 5-n Phàse transfer temperature:
1 1 0C .~: :. "
[o~]D5~ +27.61 (c - 0.039, CH2C12) NMR (CDC13) ~: 0.78-2.82 (39H, m), 3.97-4.19 (2H, m), 4.40-4.82 (1H, m), 6.77 (2H, d, J--8.4 Hz), 7.08 (2H, d, J-8.4 Hz) IR (K8r): 1758 cm 1 ~ `
Example 5 .~
: ,:-::
The optically active glycidyl ether prepared in Preparation 2, i.e. (S)-2,3-epoxypropyl 4-(trans-4-n-pentyl-cyclohexyl)phenyl ether (370 mg), potassium t-butoxide (151 mg), dimethyl methylmalonate (357 mg) and t-butyl alcohol (3 ml) were mixed, and the mixture refluxed with stirring for - 34 - - ~ ~
1331182 ~

8 hours. The reaction mixture was cooled to room temperature and 4N hydrochloric acid was added dropwise thereto until the pH
was adjusted to l. The mixture was extracted twice with ether, and the extract was washed once with a saturated saline solution and distilled under reduced pressure to remove the solvent. The residue was purified by silica gel chromatography to give Y-lactone derivatives, (2S, 4S) isomer and (2R, 4S) isomer (60 mg and 50 mg, respectively) of the following formulae:
(2S, 4S) isomer:
10n-C5H11 {~o~ ~CH3 Phase transfer temperature: 18C 54C
C SmA c - 101C >
~]D ~ +14.03 (c = 0.493, CH2Cl2) NMR (CDCl3) ~: 0.88 (3H, t, J~7.0 Hz), 0.97-1.84 (21H, m), 2.39 (lH, t, J-12.2 Hz), 2.49-2.56 (lH, m), 2.69-2.76 (1H, m), 4.04-4.12 (2H, m), 4.65-4.71 (1H, m), 6.83 (2H, d, J-8.7 Hz), 7.11 (2H, d, J-8.7 Hz) IR (KBr): 1760 cm~1 MS m/e (relative intensity, %): 359 [(M+1)+, 26], 358 [M+, 100]
Theoretical weight as C23H3403:
Calcd.: 358.2509 Found: 358.2537 . 35 ~

,, .. .~.

(2R, 4S) isomer:
n~CsH11 ~ 0 ~ CH3 Phase transfer temperature:
C > I

[~]D = +20.25 (c - 0.490, CH2Cl2) NM~ (CDC13) ~: 0.89 (3H, t, J=6.8 Hz), 0.97-1.40 (17H, m), 1.84 (3H, d, J-10.7 Hz), 2.02-2.10 (lH, m), 2.39 (1H, t, JA12.2 HZ), 2.45-2.51 (1H, m), 2.87-2.93 (1H, m), 4.01-4.12 (2H, m), 4.76-5.03 (1H, m), 6.79 (2H, d, J=8.6 HZ), 7.11 (2H, d, Ja8.6 Hz) IR (KBr): 1760 cm~1 MS m/e (relative intensity, %): 359 ~(M+1)+, 26] `
358 ~M+, 100] ~;-Example 6 The optically active glycidyl ether prepared in ;~
Preparation 5, i.e. (R)-2,3-epoxypropyl 4-(trans-4-n-propyl-cyclohexyl)phenyl ether (416 mg), potassium t-butoxide (188 mg), dimethyl methylmalonate (443 mg) and t-butyl alcohol (2.5 ml) were mixed, and the mixture was refluxed with 5tirring for 2 hour~. The reaction mixture was cooled to room temperature and 4N hydrochloric acid was added dropwise thereto until the pH was adjusted to l. The mixture was ex- ~-~
tracted three times with chloroform, and the extract was washed :~

once with a saturated saline solution and distilled under reduced pressure to remove the solve~t. The residue-was purified by .
: .. ~. ,...... ~ , , . : : : : -silica gel chromatography to give Y-lactone derivatives, (2R, 4R) isomer (77 mg) and (2S, 4R) isomer (86 mg) of the following formulae~
(2R, 4R) isomer:
n-c3H7 0~ /y~CH3 ~0 ~- :
Phase transfer temperature: 11C 17C
C~ SmA _ I :

~]D ~ -16.820 (c - 0.98, CH2Cl2) NMR (CDCl3) ~: 0.6-3.0 (23H, m), 4.0-4.2 (2H, m), 4.4-4.95 (1H, m), 6.76 (2H, d, J=8.0 Hz), 7.10 (2H, d, J=~8.0 Hz) IR (KBr): 1762 cm~1 (2S, 4R) isomer: --n-c3H7O~o ~CH3 H ~ H
Phase transfer temperature: 52C
C ~

" 0 - .
[a]D ~ -27.82 (c - 1.03, CH2Cl2) NMR (CDCl3) ~: 0.65-3.0 (23H, m), 4.0-4.2 (2H, m), 4.6-5.0 (1H, m), 6.76 (2H, d, J-8.0 Hz), 7.10 (2H, d, J-8.0 Hz) IR (KBr): 1762 cm~1 Examples 7 to 11 In the same manner as described in Examples 1 to 6, there were prepared optically active ~-lactone derivatives as ~:
shown .in Table 2, wherein R3. R4, n, m, and symbols 2* and 4* are of the following.formula: ~ -13311~2 R3~o~ocH2~CO~R4 o Table 2 No. R3 n 2' 4~ m R4 C Sm1 SmC* SmA N* I
7 n~C3H7 o S R 0 n-C9H19 . ~ , -~

11 1. R R 11 11 , __~ _ _ _ _ , .

8 n-C5H11 _ R S _ C2H5 , __~ _ _ _ _ , 11 tl S S 1. 11 ~
_ _ .~ -:

9 n~C5H11 11 R S ll n-C11H23 122 11 11 S S 11 ll ~ ,, , ' 10 n-CgH19 1t R S ll CH3 , __~, - _ _ _ , ~
ll 11 S S ll 11 ~ --3' -- -- --` _ 1~
. :: ~ ~

11 n-C9H19 n R S n n-C5H11 , __~ _ _ _ _ , __ S S _ ~ - - _ _ , Example 12 The R isomer o~ glycidyl ether prepared in Prepara- : :~
tion 5 (380 mg), dimethyl malonate (274 mg), potassium t-butoxide (163 mg) and t-butyl alcohol (2 ml) were mixed, and the mixture was refluxed with stirring for 2 hours. The reaction mixture was cooled to room temperature and 4N hydro-chloric acid was d_opwise added thereto until the pH was adjusted to l. The mixture was extracted three times with chloroform, the extract washed with a saturated saline solution, dried over anhydrous magnesium sulfate and distilled under re-duced pressure to rera~ve the sol~ent. The residue was purified by silica gel chromatography to give 4R isomer of methoxy- -carbonyl-Y-lactone derivative (220 mg) of the following ~;
formula~

n~C3H7 O~o--~C02cH3 O
IR (KBr): 1781, 1744 cm~1 The above Y-lactone derivative (200 mg), magnesium cP.loride (232 mg), dimethylacetamide (1.5 ml) and water (0.5 ml) were mixed and the mixture was refluxed with stirring fox 10 hours. The reaction mixture was cooled to room tempera- -~
ture and extracted twice with chloroform. The extract was washed with a saturated saline solution, dried over anhydrous magnesium sulfate and distilled under reduced ~-pressure to remove the solvent. The residue was purified by sllica gel chromatography to give 4R isomer of Y-lactone de~ivative (145 mg) of the following formula:
- n-C3H7 O~(~ -~co : ~
., ,, . :,: :. . - .~ . -133~1~2 Phase transfer temperature:
C > I

[a]3D = -18.640 (c z 1.27, CH2Cl2) ;
NMR (CDC13) ~: 0.65-3.45 (21H, m), 3.90-4.30 (2H, m), 4.55- ~ ;
5.00 (1H, m), 6.77 (2H, d, J=9.0 Hz), 7.11 (2H, d, J=9.0 Hz) IR (KBr): 1778 cm 1 ~ .
Example 13 The S isomer of glycidyl ether prepared in . :;~
Preparation 3 (370 mg), diethyl n-propylmalonata (442 mg), ..
potassium t-butoxide (134 mg) and t-butyl alcohol (3 ml) were mixed and the mixture was refluxed with stirring for lO hours.
The reaction mixture was cooled to room temperature and 4N
hydrochloric acid was dropwise added thereto until the pH was adjusted to l. The mixture was washed with water and methanol to lS give white crystals.. TIle Froduct was separated and purified by ~.
silica gel chromatography to give Y-lactone derivatives, (2S, 4S) isomer (240 mg) and (2R, 4S) isomer (140 mg) of the .~.
following formulae:
(2S, 4S) isomer: .:. .
n- C8H1 7 ~ /;~K3 K7 ~n Phase transfer temperature: . :
C > I

~a]D ~ +32.67 (c ~ 1.081, CH2Cl2) '` 25 NMR (CDC13) ~: 0.70-3.00 (27H, m), 4.00-4.25 (2H, m), 4.40- ~
4.85 (1H, m), 6.60-7.60 (8H, m) ., IR (KBr): 1762 cm~1 Y.' , .,~. : , ,. ~,. ~: . . - ,.
-i,~
j:", ~ . " ~, ;.. ,.: :: :;~ :

I` - 40 -1~311~2 (2R, 4S) isomer:
n-CgH17 ~ 0 ~ C3H7-n Phase transfer temperature:
C ~ I

[~]D = +22.50 (c = 0.504, CH2Cl2) NMR (CDCl3) ~: 0.70-3.00 (27H, m), 4.00-4.25 (2H, m), 4.50-5.00 (1H, m), 6.60-7.60 (8H, m) IR (KBr): 1762 cm~1 Example 14 - The S isomer of glycidyl ether prepared in Preparation 4 (260 mg), dimethyl n-octylmalonate (269 mg), potassium t-butoxide (90 mg) and t-butyl alcohol (2 ml) were mixed and the mixture was refluxed with stirring for 13 hours. After the reaCtion, the reaction mixture was treated in the same manner as described in Example 13 to give white crystals. The product was separated and purified by silica gel chromatography to give a Y-lactone derivative, (2S, 4S) isomer (43 mg) of the following formula:

n-C8H17 ~ 0 ~ C8H17-n Phase transfer temperature:
C ~ I

[~]3 - +28.59 (c - 0.674, CH2Cl2) -NMR (CDCl3) ~: 0.70-2.95 (37H, m), 3.80-4.20 (4H, m), 4.45-4.90 (1H, m), 6.90 (4H, d, J-9.0 HZ), 7.42 (4H, d, J-9.0 Hz) ~ ::

,'t . .~
~'.~': :. ' : ~ ': `:. :' ` ''' i ~ r '' ' ' ' ' " ' ~.
IR (KBr): 1760 cm~
Example.15 .
In the same manner as described in Example 13 -except that the R isomer of glycidyl ether prepared in ~.
Preparation 6 was used as the optically active glycidyl ethex .~
and dimethyl n-butylmalonate was used instead of dimethyl n- -:
propylmalonate, there were prepared ~-lactone derivatives, (2R, 4R) isomer and (2S, 4R) isomer of the following formulae: ;~
t2R, 4R) isomer: :-~
n-C12H25 ~ 0 ~ C4H9-Phase transfer temperature:
C ~ I .
130C ~:
[~]3D ~ -28.560 (c = 1.06, CH2Cl2) :~
NMR (CDCl3) ~: 0.85-2.69 (37H, m), 4.15-4.18 (2H, m), 4.71-4.77 (1H, m), 6.95-7.53 (8H, m) :~
IR (KBr): 1764 cm~1 .
(2S, 4R) isomer: -n-C12H25 ~ ~ C4H9~n Phase transfer temperature: :
C ~ I
128OC .
~]3D ~ -22.98 (c ~ 1.07, CH2Cl2) NMR (CDC13) ~: 0.85-2.85 (37H, m), 4.08-4.21 (2H, m), 4.81-4.86 (1H, m), 6.93-7.52 (8H, m) IR (KBr): 1760 cm~1 '~ .

~5 .. ~

Examples 16 to 22 :~
In the same manner as described in Examples 13 and 14, there were prepared optically active ~-lactone derivatives as shown in Table 3, wherein R3, R4, n, m, and symbols 2* and 4* are of the following formula~

R3~(O)n ~ OCH2 ~ (Co)m-R4 ~0 Table 3 No ¦ n 2* 4* m R4 C Sm1 SmC* SmA N* I
_ 16 n-C6H13 O R S O CH3 . ___~ - _ _ _ , 15 1~ ll S S 1~ 1- , ___~ - - _ _ , 17n-C6H13--R S _ n-C6H13. ___~ - - _ .
~- S S ll ~ ~_ _ _ _, _ . 140 n-C6H13 ,~ R S " n-C10H21 . __~ - - _ _ , 18 1~ .~ S S 1- 1- , 5 _ _ _ _ , , 19 n-C8H17 " R S n CH3 , __~ _ _ _ _ , .. ~ S S - - " ~ .
_ _ 127 :~
- to be continued - ~:

t ~

: :~
43 _ ~ ~

1331182 ;`:
Table 3 (continued) Ex.R3 n 2* 4* m~4 C - Sml SmC* SmA N* I
No. . ~ ~:
_ 20n-C8H17 O R S On-C9H19 . ~ _ _ _ _ , ll .. S S ,- " .~_ _ _ _ , i: ' 21n-C8H17 ll R S "n-C12H25 . _~ _ _ _ _ , ;:~ :
ll ll S S ll ." .~"_ _ _ _, _ .
22n-C8H17 1 R S llCH3 ~ _ _ _ _ , ll ll S S ll ll . _ ~ _ _ _ _, _ 119 Example 23 lS In the same manner as described in Example 12 except that the S isomer of glycidyl ether prepared in Preparation 11 (365 mg), dimethyl malonate (232 mg) and potassium t-butoxida (138 mg) were used, there was prepared 4S
isomer of 2-(methoxycarbonyl)-Y-lactone derivative t226 mg) of the following formula: ~ .
n C6H13~ ~,c02CH3 ~ :
H o IR (KBr): 1740, 1768 cm~1 The Y-lactone derlvative of the above formula was hydrolyzed and decarboxylated in the same manner as :
described in Example 12, to prepare 4S isomer of ?f_ ~

~ 44 - .:
1 3 3 1 1 ~ 2 lactone derivative (145 mg) of the following formula~
n-C6H13 ~ ~ 0 Phase transfer temperature:
C ~ I
138C -:
~]3 , +19.16 (c = 1.03, CH2Cl2) NMR (CDCl3) ~: 0.80-1.75 (llH, m), 2.15-2.85 (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 24 The S isomer of glycidyl ether prepared in Preparation 8 (518 mg), dimethyl n-octylmalonate (1170 mg) and potassium t-butoxide (269 mg) were dissolved in dimethyl-formamide (5 ml) and t-butyl alcohol (5 ml), and the mixture .
was heated with stirring at 90C for 5 hours. After the reaction, the reaction mixture was treated in the same manner as described in Example 13 to give Y-lactone derivatlves (742 mg) of the following formulae. The product was a : :
mixture of diastereomers and was. purified by silica gel chromatography to give (2S, 4S) isomer and (2R, 4S) isomer.
(2S, 4S) iso~er:
n-C8H17 ~ \ ~ ~ 8H17-n Phase transfer temperature: 152C 1850C
C ' ~ SmC* ~ I . .

, ~

,,~.~ . . . : -: :

~ 45 1331182 ~ ~

[C']D = +19.45 (c = O.613, CH2Cl2) NMR (CDCl3) ~: 0.4-3.0 (35H, ~), 3.7-4.3 (4H, m), 4.71 (1H, -m), 7.00 (4H, d, J=9.0 HZ), 7.50 (2H, d, J=9.0 HZ), 8.39 (2H, d, J-9.0 HZ), 8.89 (2H, s) IR (nujol): 1778 cm 1 ~- ;
(2R, 4S) isomer:
n-C8H1 70~{N\)~O/~C8H1 7-Phase transfer temperature: 11 2C 198C
c c SmC* ~

~ a ] D ~ ' 7 - 09 ( c ~ 0.115, CH2C l 2) ~ :
NMR (CDCl3) ~: 0.4-3.0 (35H, m), 3.7-4.3 (4H, m), 4.82 (lH, m), 7.00 (4H, d, J39.0 Hz), 7.50 (2H, d, J~9.0 HZ), 8.39 (2H, d, J-9.0 HZ), 8.85 (2H, s) IR (nujol): 1778 cm~1 Example 25 ;
The S isomer of glycidyl ether prepared in Preparation 7 (1.0 g), dimethyl n-butylmalonate (1.056 g) and pota~sium t-butoxide (63 mg) were dissolved in dimethyl- -formamide (10 ml) and t-butyl alcohol (10 ml), and the :~
mixture was heated with stirring at 90C for 2 hours. After :
I the reaction, the reaction mixture was treated in-the same manner as described in Example 13 to give Y-lactone deriva~ives (626 mg). The product was a mixture of ~" , ~
l ~J;

46 :

diastereomers and was purified.by si~ic~ gel ch~amatosra~hy ~ :
to give (2S~ 4S).isomer and (2R~ 4S) isomer.
,_ _ (2S~ 4S) isomer:
n-C8H170 ~ \ ~ 0 ~ 4H9 -n .

Phase transfer temperature:
C ~ I

[a]D - +41~04 (c a 0~137~ CH2Cl2) NMR (CDC13) ~ 0~4~3~1 (27H~ m), 3~9~4~3 (4H~ m), 4~66 (1H~
lOm), 6~92 (2H~ d, J=9~0 Hz)~ 8~25 (2H~ d, J-9~0 Hz), 8~35 (2H~ s) IR (nujol): 1776 cm~1 (2R, 4S) isomer:
~ N~ ~ 0"~ "~ ~ C4H9-n n-C8H170 ~ N ~ H 0 ~ H
~. ~
Phase transfer temperature: :
C - ~ I

~a]D7~ l25~02 (c ~ 0~23~ CH2Cl2) NMR (CDCl3) ~ 0~4~3~1 (27H~ m), 3~9~4~3 (4H~ m), 4~77 (1H~
20m), 6~92 (2H~ d, Ja9~0 HZ)~ 8~25 (2H~ d, J~9~0 Hz)~ 8~35 (2H~ s) IR (nujol): 1776 cm~
Example 26 . . In the same manner as described in Example 25 25except that the S lsomer of glycidyl ether prepared in Preparation 10 was used as the optically active glycidyl :

., -~ _ 47 _ ~
~3311~2 :
ether and dimethyl n-dodecylmalonate was used instead of ~ .
dimethyl n-butylmalonate, there were prepared Y-lactone derivatives, (2S, 4S) isomer and (2R, 4S) isomer. :~
(2S, 4S) isomer:
n-c1oH21~p~>~o/~c12H2s-n Phase transfer temperature:
C > I

[a]D = +26.01 (c = 1.062, CH2Cl2) NMR (CDCl3) ~: 0.5-2.9 (49H, m), 4.19 (2H, m), 4.82 (1H, m), .
6.95 (2H, d, J=9.0 Hz), 8.32 (2H, d, J=9.0 Hz), 8.52 (2H, s) ~
IR (nujol): 1778 cm 1 ~ :
(2R, 4S) isomer:

10 21 {-N ~ ~ C12H25-Phase transfer temperature: ;
C ~ I

[a]3D ~ +17.12 (c - 0.398, CH2Cl2) -NMR (CDCl3) ~: 0.5-2.9 (49H, m), 4.19 (2H, m), 4.81 (1H, m), 6.95 (2H, d, J-9.0 Hz), 8.32 (2H, d, J=9.0 Hz), 8.52 (2H, s) 20 IR (nujol): 1778 cm~1 ~ ;
Example 27 The S isomer of glycidyl ether prepared in :~
Preparation 9 (320 mg), dimethyl n-hexylmalonate (406 mg) :~
and potassium t-butoxide (116 mg) were dissolved in t-butyl alcohol (3.5 ml), and the mixture was refluxed with stirring -~" ;~ " ~ "~ ~ ~c ~

~ - 48 -13311~2 for 6 hours. After the reaction, the reaCtion miXtUre was treated in the 9ame manner as described in Example 13 to give a mixture of diastereomers of Y-lactone derivative (270 mg, (2S, 4S)~(2R, 4S) - 9/1).
(2S, 4S) isomer:
n-C8H17 ~ \ ~ 0 ~ 6H13-n (2R, 4S) isomer:

n~C3H17 { ~ ~ 0 ~ C6H13-n Physical properties of the mixture:
Phase transfer temperature:
C ~ I

[~]D ~ +37 93 (c ~ 1.024, CH2Cl2) NMR (CDCl3) ~: 0.50-2.80 (33H, m), 4.10-4.25 t2H, m), 4.45-4.85 (1H, m), 6.95 (2H, d, J-9.0 HZ), 8.34 (2H, d, J-9.0 HZ), 8.52 (2H, s) IR (nu jol ): 1778 cm~1 Examples 28 to 33 In the same manner as described in Examples 24 to 27~ there were prepared optically active y-lactone derivatives as shown in Table 4, wherein R3, R4, n, e, m and the symbolq 2* and 4* are of the follow~ng formula:

R3~(0)n ~ N\ ~ OCH2 ~ (Co)m-R4 N 0 ~

'.

,.. ,.. :'.` ~"` '' ~ . ~ ~ ~ ' ; ~
.'.~' l ~ ~.;

~ ~ ~ ~ !~ ~
L'~ ~_~ ~
~ ~ = e u :: . ~ ~:
_ er E ~ = = - = = = =
~ u~ tn tn u~ u~ u~ . ~
~`1 t~ u~ ~: tn ~ u~ ~
o - _ - _ _ _ _ ''; " ;'-' rl ~ ~ ~
~r tD _ ID ~ _' C.C~ . . ~ =

. . . r C
,yO :~ ~ ~ '. ~'~

1331182 ~ :

_ , . .
~ . . . . . ., E ., . l l ~ .
e ~ ~ . ~ ~.
. . l l ~ ~ lo ~ ;s~

_~
~ l ~
. ..
u~ e ~ = = = . ~.
~ ~ ~n ~o ~n ~n -,:
.~ ~: ~n c: ~n :
~ . ., ~.
U _ _ ~ I~ :C~' ,~ .
~ ~ = - ~ =_ ~ .
l l . .. ,,~
. . .
X ~ ~ .~
~ Z r~ ~ ,."

` 1331~2 The Y-lactone derivative (2S, 4S) prepared in Example 32 was sealed in a cell made of glass (thickness of - :
spacer: 22 ~m). The cell was char;3e;l wi~ll an ~l~ernating current (70 Hz, 1V), and the relative dielectric constant wa~ measured by a bridge method. The results are shown in accompanying Fig. 2. It is clear from the test results that ~:
the compound has ferroelectric properties.

.
.
,.

:,

Claims

Claims:

1. An optically active glycidyl ether of the formula:

(B) wherein R1 is a group selected from the group consisting of , and ;

n and e are each independently 0 or 1; R3 is an alkyl group having 1 to 15 carbon atoms; and the symbol * denotes an asymmetric carbon atom.