JPH0324036A - Optically active compound and liquid crystal composition - Google Patents

Abstract

NEW MATERIAL:An optically active compound expressed by formula I (R is <=20C asymmetric alkyl; Q is COO, OCO or single bond; X is H, OH or halogen; Y is <=5C alkyl, <=5C alkoxy, CF3 or halogen; k and 1 are 0 or 1; m is integer of 1-20; i and j are integers of 0-3; C* is asymmetric carbon atom). EXAMPLE:(S,S)-4-(1-Methyl-2-butyloxy)ethoxybenzoic acid 4-3-hydroxy4-(2- methylbutyloyl)phenyl phenyl. USE:A chemically stable and optically active compound capable of giving a ferroelectric liquid crystal composition having large spontaneous polarity, long spiral pitch and broad temperature range of chiral smectic C phase and respon sible at a high speed by blending with other liquid crystal compound. PREPARATION:A compound expressed by formula II (R* is optically active alkoxyalkyl; Ph is 1,4-phenylene) is reacted with a compound expressed by formula III to provide the compound expressed by formula IV in formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a novel optically active compound and a liquid crystal composition using the same.

[Conventional technology]

Liquid crystal display elements have features such as low running voltage, low power consumption, thin shape, and large eaves, and are used in calculators, watches, televisions, etc. Currently, nematic liquid crystals are the most widely used display materials for these display materials, but the response speed of image display is slow (a
10 msec. ) had a drawback. As one of the methods to solve this drawback, a display method using ferroelectric liquid crystal is proposed by N.J. A. Clark et al. [Applied Phys.
Lett. , 36, 899 (1980)]. This method utilizes the chiral smectic C phase (hereinafter abbreviated as "Sc" phase) of ferroelectric liquid crystal, and the ferroelectric liquid crystal material must exhibit ferroelectricity over a wide temperature range, including room temperature. , ■ have a reasonable tilt angle, ■ have a large spontaneous polarization, ■ have a low rotational viscosity, ■ exhibit a long helical pitch, ■ be chemically stable, etc.However, There is no known ferroelectric liquid crystal compound that satisfies all of these conditions.For this reason, when ferroelectric liquid crystal is to be put to practical use as an electro-optical element, several types of liquid crystal compounds must be mixed and used as an introduction product. There is a need.

In order to obtain a chiral smectic C (Sc") liquid crystal composition, there is a method of mixing a plurality of compounds exhibiting an Sc" phase, and a liquid crystal compound or liquid crystal exhibiting a non-optically active smectic C phase (hereinafter abbreviated as Sc phase). There is a method of adding an optically active compound to the composition, and the latter method is currently becoming mainstream because it is thought to have a low viscosity and easy to obtain a high-speed response. As optically active compounds to be added,
It is desirable for the composition to have a large spontaneous polarization and be excellent in other properties, especially a long helical pitch.

(Object of the Invention) The present inventors aimed to synthesize an optically active compound that gives large spontaneous interpolation and a long helical pitch when added to a smectic C (Sc) liquid crystal composition.
In addition, we aim to provide a new ferroelectric liquid crystal material that has a wide temperature range in the Sc' phase and responds quickly.
The present invention was achieved by searching for various optically active compounds.

(Structure of the Invention) The present invention relates to the general formula (I): (wherein, R is an asymmetric alkyl group having 20 or more carbon atoms, Q is -coo-, -oco-, or a single bond, and X is a hydrogen atom,
hydroxyl group or halogen atom, Y represents an alkyl group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, a CF group, or a halogen atom, k and l are 0 or 1, m is an integer from 1 to 20, i and j is an integer from 0 to 3. Chiral smectic C characterized by containing an optically active compound represented by 8), which also represents an asymmetric carbon atom, and one or more components of these optically active compounds.
(Sc') This is an invention of a liquid crystal composition.

In the general formula (r), the asymmetric alkyl group having 20 or more carbon atoms represented by R is preferably an alkyl group having an asymmetric carbon atom at the 11-position for the purpose of increasing spontaneous rod division, for example, 1-Methylbropyl story. 1-methylbutyl group, 1-
Specific examples thereof include methylbentyl group, 1-methylhexyl group, 1-methylhebutyl group, and 1-methyloctyl group. In addition, in order to improve liquid crystallinity, it is desirable to have an asymmetric carbon at a position away from the carbonyl group from the 2nd position onward. Examples include 2-methylbutyl group,
2-methylbentyl group, 3-methylbentyl group. Examples include 4-methylhexyl group.

The halogen atom represented by X in general formula (I) includes chlorine, bromine, fluorine, and iodine.

In general formula (I), the alkyl group having 5 to 1 carbon atoms represented by Y includes methyl group, ethyl group, brobyl group, butyl group, and amyl group, and may be either direct or branched. Examples of the alkoxy group having 5 or more carbon atoms include a methoxy group, an ethoxy group, a broboxy group, a butoxy group, and an amyloxy group, and the alkoxy group may be either straight or branched. Also, halogen atoms include chlorine and bromine. Homo,
Examples include iodine.

In the above general formula (I), when the direction of the helix induced by the asymmetric substituent H and the direction of the helix induced by the other asymmetric alkyl group/V are opposite, the helices }J cancel each other. It is expected that the helical pitch will become longer. Furthermore, when the directions of the spontaneous polarizations caused by both molecules match, it is thought that the spontaneous polarization of the entire molecule increases (for example, J.W.
．． Iiodby, E. Chin, T. M. L
cslfe, J. M. Geary, J. S. P
Argument by anel et al.
Sense and Spon-taneous
Polarization Direction in
Ferroe-Electric Smectic L
iquid Crystals” Journal
of American Ghea+ical Soci
ety, 1986. (See page 4729-4735).

For example, when R is a (S)-1-methylpropyl group, the spontaneous polarization caused is (1) and the helix is left-handed. Therefore, it is preferable that the other asymmetric alkyl group has (-) spontaneous polarization and employs a helical or Ishinomaki substituent.

As an example, (S)-1-methyl-2-ethoxyethoxy group (in general formula (I), k=1, j=l, j=0
, m=2, Y=CI+, substituent), (S)-1-methyl-2-butoxyethoxy group (in general formula (I), k=
l, i=l, j=0, m·4, Y-ell, and the like. However, for example, when a (S)-2-methylbutyl group is used as the asymmetric alkyl group R, the spontaneous polarization caused by this group is (+) and the helix is right-handed, so the other asymmetric substituent is ( S)-t-methyl-
When a 2-ethoxyethoxy group is used, the spontaneous polarizations cancel each other out. In this case, the spontaneous polarization is (◆)
．． The helix is a left-handed substituent, such as the (S)-2-methyl-2-butoxyethoxy group (in general formula (I), k
=1, i=0,. i=l, va=4, 'I'(
;tlv substituent) is preferably used.

The compound of the present invention can be synthesized, for example, by the following route.

0 first step (in the formula, R represents an optically active alkoxyalkyl group, Ts represents a p-toluenesulfonic acid residue, and pH represents a 1,4-phenylene group), that is, first, p-hydroxy Acetophenone with sodium hydride at the bottom left,
Optically active alcohols (e.g. (R)-1-methyl-2
-ethoxyethanol} with p-toluenesulfonic acid ester, and then oxidized with an aqueous sodium bromate solution to obtain an optically active para-substituted benzoic acid.

0 second step R”0-Ph-COOH + SOC+2 → R
“0-Ph-GOCI}1”0-Ph-(:OCI
+ l{0-Ph-Ph(X)-Go-R −+R”
O-Ph-COO-Ph-Ph(X)-Go-R
(IV) (In the formula, R", Ph, is reacted with an optically active phenol having a ketone group in the presence of a base such as pyridine to obtain the desired product.

The present invention will be described in more detail below with reference to Examples and Reference Examples, but the present invention is not limited in any way by these Examples and Reference Examples.

〔Example〕

Reference example 1. (S)(+)-4- {3-hydroxy-4
-(2-Methylbutyroyl)phenyl}Synthesis of phenol (1) Synthesis of 3-penzyloxyodobenzene 60%
20g (0.5 mol) of sodium hydride (oil-based) with N,
100 g of m-iodophenol was suspended in 300 nt' of N-dimethylformamide (DMF).
(0.454 mol) DMF solution was added dropwise at 70±5°C.
The mixture was stirred and reacted for 30 minutes. Then benzyl chloride 5 7.
4 g (0.454 mol) was added dropwise to 100±5°C.
I had to fight for two hours. After injecting water 11 into the reaction solution,
Extract with ethyl acetate, separate the organic layer, wash with water, and add anhydrous Mg
It was dried with SO. The desiccant was separated from the 4P, the solvent was distilled off, and the crystallized residue was re-crystallized from ethanol-1. 119.7 g of 3-penzyloxyodobenzene was obtained as a white solid. Yield: 85%. m. p. 51.0~
53.0℃.

'IINMRδppm ((;D(13): 5.
00(2tl,s,Ar-(:%O-),IR(
Knr)cm-': ! 240.

(214-(3-penzyloxyphenyl)anisole synthesis (3-penzyloxyodobenzene obtained in 11) 1
9 g (0.384 mol) and p-iodoanisole 8 9. 9 g (0.384 mol) at 60±5℃
Add 210g of FF4 powder to it and heat to
The reaction was carried out at 210°C for 10 hours. 500 rnl of toluene was injected into the reaction mixture, the impurities were separated by 4P, the solvent was distilled off, and the resulting crude crystals were separated in a column [filling material: Wako Gel C-20]
0 (manufactured by Wako Pure Chemical Industries, Ltd.); eluent; n-hexane/ethyl acetate = 20/1) to obtain 64.8 g of 4-(3-penzyloxyphenyl)anisole as white crystals.

Yield: 58%offl'f"78.5~old.0℃
, 'HNMRδppm (CDα3) + 3.83
(3H, s, Ctl, 0-), 10/1) L/, 4
15.1 g of -(3-hydroxyphenyl)anisole was obtained as white crystals. Yield: 76%. m. p.
7fi. 5-78.0℃8'HNMRδppm (
C: Dα3): 3.82 (3fl, s, C%
0-) ,IR (KBr)cm-' + 2850
．． 1240, [314-(3-Hydroxyphenyl)anisole synthesis 29.0g (0.1 mol) of 4-(3-penzyloxyphenyl)anisole obtained in (2) was mixed with 300% of a mixture of ethyl acetate and tetrahydrofuran. 2g of rane nickel dissolved in
Catalyst F was catalytically reduced (initial hydrogen pressure: 55 κg/CIII2; reaction temperature: 100±10°C), the catalyst was separated, and the solvent was distilled off to obtain crude crystals. Filler: Wakogel C-200: Eluent: n-hexane/
Ethyl acetate=IR (κOr)c+a-':
3400, 2950, 2840, 1600
.

(4) Synthesis of S(+)-4-(3-(2-methylbutyroyloxy)phenyl}anisole S(+)-(2-methyl)butyric acid 40 g (0.39
mol) and 70 g of thionyl chloride are gradually heated until 50~
The reaction was carried out at 60°C for 2 hours. After the reaction, it is concentrated, and the residue is distilled under atmospheric pressure to obtain bρ. 42 g of S(+)(2-methyl)butyroyl monochloride of the 116-118° C. fraction was obtained as a colorless oil. Yield: 90%.

Separately, 15 g (75 mmol) of 4-(3-hydroxyphenyl)anisole obtained in step (3) was dissolved in 40-pyridine, and 9.1 g (75 mmol) of the above S(+)(2-methyl}butyroyl monochloride was added to the solution. mmol) was added dropwise at 20 to 30°C, and stirred and reacted at the same temperature for 2 hours. After the reaction, dilute aqueous hydrochloric acid was injected to neutralize and extracted with ethyl acetate. The organic layer was separated, washed with water, and anhydrous. It was dried with MgSO4. After removing the desiccant, the solvent was distilled off, and the pale yellow extract of the residue was separated by column (filling material: Wakogel C-200; eluent: n-hexane/ethyl acetate = 5/1). , S (+)−4 − (
20.5 g of 3-(2-methylbutyroyloxy)phenyl}anisole was obtained as a pale yellow oil. Yield: 96%. [a lo :4-1 2. O゜
(c=2, Ctlα3).

H N M R δppm (CDCt+): 1.
03 (311, JJ・7Hz, -Cllf;H, (:
Ilff), 1.33 (3H, d, J-7HZ, -C
IICi). 1.55 to 1.97 (51S(+)-
Synthesis of 4-(3-hydroxydi-4-(2-methylbutyroyl)phenyl}anisole Nitrobenzene 15r
5.7 g of aluminum chloride was added to nl and heated to 70°C, and the S (+)-4-{3-(
2-Methylbutyroyloxy}phenyl}anisole 1
0 g (35 mmol) was added dropwise. Then 115-12
The reaction was carried out at 5°C for 3 hours. The reaction solution was poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. After separating the insoluble materials, the organic layer was separated, washed with water, and dried over anhydrous Na2S04. The desiccant was separated, the solvent was distilled off, and the obtained brown oil was separated by column (filling material: Wakogel C-200; eluent: n-hexane/ethyl acetate = 10/1) to obtain S(+)- 4-{3
3.7 g of hydroxyloxy4-(2-methylbutyroyl)phenyl}anisole were obtained as a pale yellow viscous oil.

Yield: 37%. [α]. :+19.5'( c =
2. CltC13).

? 1NMR δppm (CDα3): 0.9
6 (38,t.,.I■7flz,-Cl-C11
■cub>. 1.24 (3H, d, J・7tlZ
, -CHcII,), 1.50-1,93JR (
Neat) cm-': 3400, 2920,
1605, elemental analysis plant (C+8H2oOz) theoretical value 20%, 76.03. H%, 7.09
.

Actual value = C%, 75.85. H%, 7.1:
l.

(61 S (+) -4 - (3-hydroxy-4
-(2-methylbutyroyl)phenyl)phenol synthesis (5) S(+)-4 - {3-hydroxy-
4-(2-methylbutyroyl)phenyl}anisole 8
g (10 mmol) and 1.7 g of aluminum chloride to 307 g of toluene! The reaction was carried out under reflux for 3 hours while stirring. The reaction solution was poured into dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic layer was separated, washed with water, and dried over anhydrous Na2SO4. The desiccant was separated and the solvent was distilled off, and the obtained brown curved material was subjected to column H (filling material: Wakogel C-200; eluent: n-
Hexane/acetone = 10/1) and S (+)-4
- {3-hydroxy-4-(2-methylbutyroyl)
Phenyl} Phenol 1.7g? ? Obtained as a yellow viscous oil. Yield: 63%. [α]o: +18.5
゜ (C・2, CHα3).

'HNMRδppm ((:Dα3): 0.9
6 (3}1, t, J-7Hz, -CHGH, [;}h
), 1.25 (3H, d, J-7HZ, -CHCH2
-), 1.50-1.93(2}1,m,-(;H(
;LLCH3), 3.41-3.50 (IH. m
,-GOG! ! -), II{ (Neat)cm-'
: 3350, i960, 1610, elemental analysis value (
C+J+aO*) Theoretical value: C%, 75.53; H%, 6.71
, Actual value: C%, 75.50; H%, 6.81
.

Reference Example 21S) Synthesis of (+)-4-{4-(2-methylbutyroyl)phenyl}phenol (1) Synthesis of 4-phenylanisole 330 g (1,94 mol) of 4-hydroxybiphenyl
and 350 g of sodium hydroxide were dissolved in 6 It of water, and 55
476 g (3.77 mol) of dimethyl sulfuric acid was added dropwise at ~60°C, and the mixture was further stirred at 70°C for 30 minutes. After cooling, the precipitated crystals were collected, and the resulting crude product was recrystallized from ethanol to give 4
-182 g of phenylanisole was obtained as a white powder crystal. Yield: 52%. mp. 80.5-83.0°C.

'IINMRδppm((:DCi3) + 3.8
0(3H, s, CULL-), 6.83-7.56
(9f{, m, aromatic ring hydrogen).

Ifl(KBr)c+n-': 2950, 28
50, 1610, 1580, (21S(+)-4-
(4-(2-Methylbutyroyl)phenyl)anisole synthesis (1) 4-phenylanisole 2 6.0 g
(2-methyl ) 20.4 g (0.17 mol) of butyroyl was added dropwise, and the reaction was further stirred and refluxed for 1 hour. After concentrating the reaction solution, 250 d of diluted hydrochloric acid aqueous solution was poured and extracted with chloroform. The organic layer was separated and washed with water. After drying, the solvent was distilled off, and the obtained reddish brown semi-molten crystals were recrystallized from n-hexane-ethyl acetate to obtain S(◆)-4-(4-(2-methylbutyroyl)phenyl)anisole 12. 4 g was obtained as white crystals.

Yield: 33%. mp. 119-120℃. [α]o
:+23-1°((:-2, ellα3).

1B(KHr)co+-': 2940, 16
70, 1600. (3) S (+) −4 −
{4-(2-methylbutyroyl)phenyl}phenol Synthesis (2)
mmol) and 6.6 g of aluminum chloride in 1 toluene
The mixture was added to 20 rnl, and stirred and refluxed for 8 hours.

The reaction solution was then poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic layer was separated, washed with water, dried, and the solvent was distilled off. The resulting reddish brown oil was separated by column (filling material: Wakogel C-200; eluent: n-hexane/ethyl acetate =
10/1→5/1) and further recrystallized from n-hexane-ethyl acetate to give S(+)-4-(4-(2-
7.6 g of methylbutyroyl)phenylphenol was obtained as white crystals.

Yield: 66%. town. 95.5-98.5℃, [α]
D: +20.7° (c=2, GHα3).

C I,), 1.48-1.92 (2H, l,
-COCH (Jj, CH,), 3.41?590, Example 1. (S,S)-4-(1-methyl-2-butyroxy)ethoxybenzoic acid 4-{3-hydroxy-4
Synthesis of -(2-methylbutyroyl)phenyl}phenyl (1) R(-)-p-toluenesulfonic acid 2-hydroxybrobyl (in general formula (1), m・4,i・
0,j・o. k-Il. Q■I. Y-CI
*. Synthesis of Q-COO,
03 mol) was dissolved in pyridine 53 (lrnI!) and 15
167 g of p-}luenesulfonyl chloride was added at a temperature below .degree. C., and the mixture was stirred at the same temperature for 4 hours. After concentrating the reaction solution under reduced pressure, methylene chloride and water were added, stirred and allowed to stand to separate the methylene chloride layer, which was washed with water and then dried.

Then, the solvent was distilled off, and the resulting yellow oil was divided into column fractions 1i.
! (Filling agent: Wakogel C-Methyl chloride) to obtain R(-)-P-acid 2-hydroxyprobyl 1 as a viscous oil. Yield: 200; Eluent: 17 g of toluene sulfone, slightly yellow viscous, 58%. [α1o: 23.0 g of banol was obtained as a colorless oil.

Yield: 58%. GC-included stars: 94.6%.

[a] o: -0.7° (Neat).

? 211, m, J・7.3}1z, (:83Cl
lj-), 1.52 ~ 1.58 (211, m, J
■7.3Hz, -CH2Cll2CH20-), 2.6
5 (I!l.bs, -Oij), 3.187.83(
2H, d, . J'8Hz,7z-Lu C2. Ci)
．． (21 Synthesis of R(-)-1-n-butoxy-2-probanol.

70 g (0.3
mol) was added dropwise at 70°C, and the mixture was stirred at 5°C for 1 hour. Water was poured into the reaction solution, allowed to stand, and the layers were separated to obtain an organic layer.

The organic layer was washed with water, dried, and concentrated, and the obtained oil was distilled under reduced pressure. R of 168-169℃/760mmHg fraction
(-)-1-n-butoxy 2-broIR (Neat
．． )c+s-': 3420, 2970, 29
40, 2880.

(31 R (-) -p- toluenesulfonic acid
Synthesis of 2-(1-n-butoxy)proyl
! p-toluenesulfonyl chloride 1 by dissolving it in 15℃ or less
4.5 g (76 mmol) was added and stirred at room temperature for 4 hours. After the reaction, 300ml of diluted hydrochloric acid was poured into the reaction mixture, followed by extraction with methylene chloride. The organic layer was separated, washed with water, dried, the solvent was distilled off, and the residue was separated into a column. ! (Filling agent: Wakogel C-200
: Eluent: methylene chloride) and R(-)-p-toluenesulfonic acid 2-(in-butoxy>probyl 1)
6. 2 g were obtained as a pale yellow viscous oil. Yield: 75%. [α]o: -5.0° (Neat).

(2H, l, GH31;%-), 1.52-1.6
0 (2H, rx, -(:H2CHx). Next, 15.0 g (5
20 Fnl of DMF solution of 2.4 mmol) was added dropwise, and 8
The reaction was carried out at 0°C for 4 hours. After the reaction, 300 ml of water was injected and methylene chloride oil was discharged. The organic layer was separated, washed with water, dried, and concentrated to obtain 11.0 g of S (-)-4-(2-<1-n-butoxy)probyloxy}acetophenone as a yellow oil. Collection ■, -cloc! i! −),
4.65-4.71 (IH.m. same), 7.32 (
2H. d. J・8.4Hz, Fx-roo(;3,
G6), 7.81 (2H, d, .1-8.411
z, 7 enil (:2. CJ.fR (Neat
) cm-': 2960, 2940, 287
0, 1600, (4)S (-)-4-(2-(1
- Synthesis of n-butoxy〉probyloxy}acetophenone 2.3 g of sodium hydride and 201 g of tetrahydrofuran
p-hydroxyacetophenone 7 at room temperature into a suspension of nl
．． Add 30rnl of 2g (52.4 mmol) of DMF solution dropwise and stir at 50-60°C for 30 minutes to give a solution of 1.50-1.6
0(2H, l.-(:82CH, CH20-), 2.
55 (3H.s, -C3.GJ, 7.92(
2H, d, J-8.4tlz, Phenyl C: 2.
(:6). IR (Neat)cs-': 296
0, 2930, 2860, 1680, 16
Synthesis of 00, (51S (')-4-{2-(1-n-butoxy)propyloxy}benzoic acid S (1)-4-{2-(1-n) obtained in Section F (4)
-butoxy>propyloxy}acetophenone 13.0
An aqueous solution of sodium hypobromite (180 mmol) prepared from an aqueous solution of sodium hydroxide (34.3 g) and bromine (31.2 g) at 20-25° C. -, then 40
Stirring was carried out at ~50°C for 2 hours. After cooling, the mixture was treated with sodium bisulfite, acidified with hydrochloric acid, and extracted with chloroform. The organic layer was separated, washed with water, dried, and concentrated to obtain 10.2 g of S(-)-4-(2-(1-n-butoxy)propyloxy}benzoic acid as a pale yellow oil. Rate: 78%.

[αlo: -8.0° (C・2, CIl03). 6
．． 96 (2H, d.J, 8.8Hz, phenyl C,
, C5), 8.03 (2+1, d, J・
8.811z. Phenyl c2, cg), 1
0.24 (IH, bs, -COOH). IR (Ne
at) cab-': 3050, 2960, 2
920, 2860, 2660, 2550.
1710, 1600, (61 (S,S) −
Synthesis of 4-(1-methyl-2-butyroxy)ethoxybenzoic acid 4-{3-pidroxy=4-(2-methylbutyroyl)phenyl}phenyl S (-)-4-( obtained in (5) above) 2-(1-n
-butoxy)propyloxy}benzoin 12.5g (10
2.7 g of thionyl chloride was added dropwise at room temperature, and the mixture was stirred and refluxed for 1 hour.

After the reaction solution was concentrated to dryness, it was dissolved in methylene chloride, and the S(◆)-4-(:]monohydroxy-4-(2-methylbutyroyl)phenyl)phenol obtained in Reference Example 1 was dissolved. The mixture was poured into 7 g (10 mmol) of pyridine 301 solution and reacted at 50-60° C. for 8 hours. After cooling, the mixture was acidified with hydrochloric acid and extracted with methylene chloride. The organic layer is separated, washed with water, dried, and concentrated, and the residue is separated into a column! (Filling agent: Wakogel C-200; Eluent: n-hexane/ethyl acetate = 20/1) (twice) and (S,S) -4
- (1-methyl-2-butyroxy)ethoxybenzoin
2.4 g of 4-{3-hydroxy-4-(2-methylbutyroyl)phenyl}phenyl was obtained as a colorless viscous oil. Yield: 48%.

III(Neat)cm-': 3050, 295
0. 2920. 28B0. 1730, 1630.
+600.

Elemental analysis value (C:nLsOe) Theory: C96, 73.79. H! Ii, 7.
+9. Actual value: 20 wood, 73.94. H$, 7.1
0, Example 2. (S.S)-4- (1-methyl-2-
Butyroxy)ethoxybenzoic acid 4- (4- (2-
methylbutyroyl) phenyl} phenyl (general formula (1)
In , mountain・4, i・l, ,j−0, k・1. Mutual I, Y-CI13, Q-COO, X-11, R-
S(-)-4-(2-(1) obtained in (5) of Example 1)
- n-butoxy)propyloxy}benzoic acid 3.4g
(13.8 mmol) and S (+)− obtained in Reference Example 2
4-(4-(2-methylbutyroyl>phenyl)
The reaction and post-treatment were carried out in the same manner as in Example 1 (6) using 3.5 g (13.8 mmol) of phenyl, and after column separation, recrystallization from ethanol was performed to obtain (S,S) -
2.5 g of 4-(4-(2-methylbutyroyl)phenyl}phenyl 4-(1-methyl-2-butyloxy)ethoxybenzoate was obtained as white crystals. Yield: I
R(Neat)cm-' + 2950. 2920,
2860, 1730, 1675, l600.

Elemental analysis value (C3+IhsOs) Theoretical value: C turtle, 76.20. H'4, 7.43.
Actual value: C! I:. 76.33:H9&, 7.51
The melting point of this compound is 38°C, and it shows a smectic A phase up to 549°C. Also, when the temperature drops from 49℃ to 5.5℃
It showed a smectic A phase up to 5.5°C, and a chiral smectic C phase from 5.5°C.

This compound was sealed in a 2 μm test cell (a cell made of a glass plate coated with ITO, spin-coated with polyimide and rubbed in one direction, and then laminated at 2 μm intervals via a glass bead spacing). When a square wave was applied, a clear response was shown at 3.0°C.

Example 3. (S,S)-4-(1-Methyl-2-hexyloxy)ethokitobenzoic acid 4-{3-hydroxy-
4-(2-methylbutyroyl)phenyl}phenyl (general 2〇), m・6, i・1, j・0. k-1,
Il-L Y”Cfh, Q”COO, X・OH,
Synthesis of R-1-methylbrovir group compound (1) Synthesis of R (-)-l-n-hexyloxy-2-probanol R (-)-p - obtained in Example 1 (1) The reaction and post-treatment were carried out in the same manner as in Example 1 {2} using 70 g (0.3 mol) of 2-hydroxybrobyl toluenesulfonic acid and n-hexanol to give bp. 142-1
R (-)-1-n- of the 43°C/104mmHg fraction
35.6 g of hexyloxy-2-propanol was mixed with a colorless oil (CI12)s-), 1.24-1.72 (I
I}l,m,CH3 (C: hh1). Yield: 74%., GC content: 98.0%.

[(Xlo: -1.1' (Neat).

1.40 (6H, ffi, CIl 3CJCH
, C:jl-), 1.5:l ~1.61(2H,
IR(Neat) cm-': 3420, 296
0, 2940, 2870, (2) R (-)-P
- Synthesis of 2-(1-n-hexyloxy)probyl toluenesulfonic acid R(-)-1-n-hexyloxy- obtained in (1) above
The reaction and post-treatment were carried out in the same manner as in Example 1 (3) using 15.0 g (92.5 mmol) of 2-probanol, and R(-)-ρ-toluenesulfonic acid 2- (1-n- 23.2 g of (xyloxy)probyl were obtained as a slightly yellow viscous oil. Yield: 80%.

[a] o: -6.1” (Neat).

'IINMRδppm (CDα3): 0.89
(38, t, J・6.641x, CtL+d, J=8.
4Hx. 7z Nilu C3, C,), 7.81 (2
tl, d, J・8.4Hz, Phenyl C2. Ce
). IR(Neat)cm-': 2960, 2940
, 2860, 1600.

(3) Synthesis of S(-)-4-(2-(1-n-hexyloxy)probyloxy}acetophenone R(-)-p-toluenesulfonic acid 2-(1) obtained in Section E (2) -n-hexyloxy)provil 15.0g (
4 7. The reaction and post-treatment were carried out in the same manner as in Example 1 (4) using S(-)-4).
2.6 g of -(2-(1-n-hexyloxy>probyloxy)acetophenone 1) was obtained as a slightly yellow oil.

Yield: 95%. [αIn :-9.1° (c=2
, CHα3).

IHNMRδppm (CDα3): 0.87
(3H, t, J-6.6Hz, Oh(12) S-)
, 1.27-1.40 (9H, rs, CH3(C
Hxl2-and? ! i. i −(:I+−), 1.51 to 1.60 (2L m, −C
ijzCH20-), 2.55 (3H,s, tlJ
j, GO-), 3.45 to 3.77 (4H, I, -C
HOG%-), 4.6lq113 to 4.68 (Ill,m,-(:fl-), 6.95
(2H.d.J・8.4Hz, Phenyl C3
．． 05), 7.92 (2}1, d, J・8.41l
z, phenyl G2. C6).

IR(NeaL)all-': 2960, 293
0, 2860, 1680, 1600, (4)
Synthesis of S(-)-4-(2-(J-n-hexyloxy)probyloxy)benzoic acid S(-)-4-(2-(1-n-) obtained in (3))
hexyloxy)propyloxy}acetophenone 12
．． The reaction and post-treatment were carried out in the same manner as in (5) of Example 1 using 0 g (43 mmol), and S(-)-4-(2-
10.8 g of (1-n-hexyloxy)probyloxy}benzoic acid was obtained as a slightly yellow oil.

Yield: 89%. [α]. :-8.7゜(C・2.1,
CHα3).

I HNMR δppI! + (CDα3): 0
．． 87 (3N, t, J-6.6Hz, C% (2H,
d, J・8.8Hz, 7x Nilu CS, C
．． ), 8.03 (2H, d, J=8.8Hz,
Phenyl(;2, c6), 9.23(IH, b
s, -(1:00ji). IR(Neat)cm-'
: 3060, 2930, 2850, 2660
, 2550, 1710, 1600, (5) (5.5) -4'- (1-Methyl-2-hexyloxy)ethoxybenzoic acid 4-{3-hydroxy-4-(2-methylbutyroyl)phenyl} Synthesis of phenyl S (-)-4-(2-(1) obtained in Example 3 (4)
- n -hexyloxy)propyloxy}benzoic acid 2.8 g (10 mmol) and S (+
)-4-{3-Hydroxy-4-(2-methynolebutyroinolenphenyl}phenol 2.7 g (10 mmol) was used for reaction and post-treatment in the same manner as in (6) of Example 1, (S,S) - 4 - (1-methyl-
1.1 g of 2-hexyloxy)ethoxybenzoic acid 4-{3-hydroxy-4-(2-methylbutyroyl)phenyl}phenyl was obtained as a colorless viscous oil. Yield: 2
1%.

? R(Neat)cr': 3050, 2950
, 2920. 2860. 1730, +630
．． 1600. , Elemental analysis value (C**H4.06) Theoretical value: CJ, 74.41; H96, 7.57
.

Actual measurement value: C zero, 74.32; H turtle, 7.79, Example 4. (S,S) -4-(1-methyl-2-hexyloxy)ethoxybenzoic acid 4-(4-(2-methylbutyroyl)phenyl)phenyl (in general formula (I), a+J, i-1 , ,i・0, k■l, J
2■1, Y-G■3, q-(:00, X-11,
Synthesis of R-1-1 tilbrovir group compound) SN-4-(2-(1-
n-hexyloxy)propyloxy}benzoic acid 3.9
g (14 mmol) and S(+)-4- obtained in Reference Example 2
(4-(2-methylbutyroyl)phenyl}phenyl 3
．． The reaction and post-treatment were carried out in the same manner as in Example 1 (6) using 5 g (14 mmol), and after column separation, recrystallization from ethanol gave (S,S)-4-(1-methyl-2 -hexyloxy)ethoxybenzoic acid 4- (4-
(2-methylbutyroyl)phenyl}phenyl3.1
g was obtained as white crystals.

Yield: 43%. mp. 34.0-37.5℃. IR
(Neat)c-+ 2950. 2910, 28
50, 1730, 1675, 1600 o Elemental analysis value (G1*Hao05) Buron I〆5: C%, 76.7+. H%,
7.80, actual value: (J, 76.74:H%i
．． 7.71, this compound showed a smectic A phase in the range 49-50°C and an unidentified smectic phase at temperatures below 49°C.

Example 5.

10% of each of the compounds obtained in Examples 1 to 4 was added to Merck's Smectic C liquid crystal composition Z L 1 3234B.
was added, and the liquid crystal temperature was measured. In addition, these compositions
A test cell (ITO-deposited glass plate spin-coated with polyimide and rubbed in one direction) was sealed in a cell made of glass beads laminated at intervals of 2 μm via a glass bead, and the characteristics were measured. Results are shown in Table 1.For comparison, Table 1 also shows the existing optically active compound (S)-4-(4-nonyloxyphenyl)benzoic acid.
The results when using 3-hydroxy-4-(2-methylbutyroyl)phenylene are also shown. In the table, the response time is the time required for the transmittance to change from 0 to 90% when a square wave of ±IOV is applied, and the pitch is the chiral nematic phase (
The helical pitch in the N'' phase is shown. Characteristics other than pitch are the values at 30°C.

In addition, in the table, Sc' is chiral smectic C phase, SA
indicates a smectic A phase, Nl indicates a chiral nematic phase, ■ indicates an isotropic liquid phase, and ● indicates the presence of that phase. Also, 1 indicates that the phase does not exist.

As is clear from Table 1, the compounds of the present invention have a higher spontaneous dissociation,
It can be seen that the helical pitch is large and the response is fast.

Table 1 When tA+ is different, a long helical pitch can be obtained in the ferroelectric liquid crystal composition.

Claims (2)

[Claims] (1) General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an asymmetric alkyl group with 20 or less carbon atoms, Q is -
COO-, -OCO-, or a single bond, X is a hydrogen atom,
hydroxyl group or halogen atom, Y represents an alkyl group having up to 5 carbon atoms, an alkoxy group having up to 5 carbon atoms, a CF_3 group or a halogen atom, k and 1 are 0 or 1, m is an integer of 1 to 20, i and j is an integer from 0 to 3. Further, C^* represents an asymmetric carbon atom. ) is an optically active compound represented by (2) A chiral smectic liquid crystal composition containing one or more components of the optically active compound according to claim (1).