JPH06321869A - Optically active alkanoic acid ester derivative having aromatic substituent and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new compound exhibiting chiral smectic phase in a wide temperature range including room temperature range and useful as a ferroelectric liquid crystal display material. CONSTITUTION:The compound of formula I [R<1> is 1-20C alkyl; R<2> is 1-10C alkyl; R<3> is 1-20C (alkoxy)alkyl; (n) is 1 or 2; C* is asymmetric carbon], e.g. 4-octoxyphenyl (S)-4-[1-(butoxycarbonyl)ethyl]benzoate. The compound of formula I can be produced by reacting a compound of formula II (X is OH or halogen) with a compound of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel optically active aromatic group-substituted alkanoic acid ester derivative and a process for producing the same. The aromatic group-substituted alkanoic acid ester derivative of the present invention is particularly useful as a material for displaying a ferroelectric liquid crystal.

[0002]

2. Description of the Related Art Liquid crystal display devices are widely used because they operate at a low voltage, consume little power, and can be displayed in a thin shape. The most commonly used liquid crystal display element at present is one using a nematic liquid crystal, which has a slower response speed as compared with the light emitting display system, and when the applied voltage is cut off, the display memory is not stored. There are also drawbacks such as not being able to be obtained. Therefore, various attempts have been made to improve these drawbacks. For example, the STN (Super Twisted Nematic) system, which is a simple matrix drive, uses a retardation film, which is lighter and cheaper. However, the response speed is still insufficient. Further, an active matrix method such as a TFT (thin layer transistor) in which a switching element is arranged for each pixel has begun to be put into practical use due to the progress of ultra-high-definition element forming technology, but there is still a limit to increasing the capacity.

A surface-stabilized display method using a ferroelectric liquid crystal reported by Clark et al. (Appld.
Phys. Lett., Vol. 36, p. 899, 1980) has been attracting a great deal of attention because it is characterized by having a simple matrix drive, high-speed response and memory, and is likely to have a large capacity. . In this case, the liquid crystal phase of the ferroelectric liquid crystal used is a low-viscosity and ferroelectric chiral smectic C phase (hereinafter referred to as S _C
* Abbreviated as phase. ) Is preferable, and the ferroelectric liquid crystal having the S _C * phase is used alone or as a dopant (Mol. Cryst. Liq. Crys) to the mother liquid crystal having the low viscosity S _C * phase.
, 89, 327-328, 1982), but in any case, the S _C * phase may exist in a wide temperature range including the room temperature range. Required.

Conventionally, some optically active aromatic group-substituted alkanoic acid ester derivatives which are liquid crystal compounds exhibiting the S _C * phase are known (for example, JP-A-2-45449 and JP-A-2-67251). No.), the S _C * phase of these compounds is in a relatively high temperature range not including the room temperature range,
The temperature range was also narrow.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel optically active aromatic group-substituted alkanoic acid ester derivative containing a room temperature range and exhibiting an S _C * phase in a wide temperature range, and a method for producing the same. It is a thing.

[0006]

The present invention provides the following general formula (I)

[Chemical 4] [In the general formula (I), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents an alkyl group having 1 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms or Represents an alkoxyalkyl group, n represents 1 or 2, and C * represents an asymmetric carbon atom. ] It is related with the optically active aromatic-group substituted alkanoic acid ester derivative represented by these.

In the general formula (I), R ¹ has 1 to ¹ carbon atoms.
Examples of the alkyl group of 20 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
There are dodecyl group, tridodecyl group, and branched isomers thereof.

Examples of the alkyl group having 1 to 10 carbon atoms for R ² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and their groups. There are branched isomers, etc.

Examples of the alkyl group having 1 to 20 carbon atoms of R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Dodecyl group, tridodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group,
There are eicosanyl groups, and branched isomers thereof. Further, R ³ has an alkoxyalkyl group having 1 to 20 carbon atoms (-Y
Represented as OR ⁴ . ), An alkoxymethyl group, an alkoxyethyl group, an alkoxypropyl group, an alkoxybutyl group, an alkoxypentyl group, an alkoxyhexyl group, an alkoxyheptyl group, an alkoxyoctyl group, an alkoxynonyl group, an alkoxydecyl group, an alkoxyundecyl group, an alkoxy group. Dodecyl group, alkoxytridodecyl group, alkoxytetradecyl group, alkoxypentadecyl group, alkoxyhexadecyl group, alkoxyheptadecyl group, alkoxyoctadecyl group and alkoxynonadecyl group (wherein R ⁴ is a methyl group, an ethyl group, a propyl group Group, butyl group, pentyl group, hexyl group,
A heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridodecyl group, or a branched isomer group thereof, and the like, and the alkoxyalkyl group does not exceed 20 carbon atoms).

Specific examples of the optically active aromatic group-substituted alkanoic acid ester derivative represented by the general formula (I) of the present invention include the following. 4-hexoxyphenyl (R) -4- [1- (butoxycarbonyl) methyl] benzoate, 4-octoxyphenyl (S) -4- [1- (butoxycarbonyl) ethyl] benzoate, 4-nonoxyphenyl ( R)-
4- [1- (methoxycarbonyl) ethyl] benzoate, 4-decyloxyphenyl (S) -4- [1- (propoxycarbonyl) ethyl] benzoate, 4-decyloxyphenyl (R) -4- [1- (Isobutoxycarbonyl) decyl] benzoate, 4-dodecyloxyphenyl (S) -4- [1- (octoxycarbonyl) ethyl] benzoate, 4- (2-methyl) decyloxyphenyl (R) -4- { 1-[(3-Methoxy) propoxycarbonyl] octyl} benzoate, 4-octadecyloxyphenyl (S) -4- [1- (hexoxycarbonyl) propyl] benzoate, 4- (4'-pentoxybisiphenyl) (R) -4- [1- (isobutoxycarbonyl) decyl] benzoate, 4- (4′-
Octoxybiphenyl) (S) -4- [1- (propoxycarbonyl) ethyl] benzoate, 4- (4'-
Octoxybiphenyl) (S) -4- [1- (butoxycarbonyl) ethyl] benzoate, 4- (4'-octoxybiphenyl) (S) -4- [1- (hexoxycarbonyl) ethyl] benzoate, 4 -(4'-octoxybiphenyl) (S) -4- [1- (octoxycarbonyl) ethyl] benzoate, 4- (4'-nonyloxybiphenyl) (R) -4- [1- (methoxycarbonyl) Ethyl] benzoate, 4- (4'-tetradecyloxybiphenyl) (R) -4- [1- (octoxycarbonyl) ethyl] benzoate, 4- [4 '
-(2-Methyl) decyloxybiphenyl] (S) -4
-{1-[(3-ethoxy) propoxycarbonyl] octyl} benzoate, 4- [4 '-(3-methyl) nonyloxybiciphenyl] (R) -4- [1- (ethoxycarbonyl) ethyl] benzoate, 4- (4'-tetradecyloxybicyclophenyl) (S) -4- {1-
[(2-Propoxy) ethoxycarbonyl] nonyl} benzoate, and 4- (4'-eicosanyloxybicyclophenyl) (R) -4- [1- (decyloxycarbonyl) isobutyl] benzoate.

The present invention also relates to a process for producing an aromatic group-substituted alkanoic acid ester derivative represented by the general formula (I). The aromatic group-substituted alkanoic acid ester derivative of the general formula (I) has the general formula (II)

[Chemical 5] [However, in general formula (II), R ² , R ³ and C * have the same meanings as in general formula (I), and X represents a hydroxyl group or halogen. ] The compound represented by the general formula (II
I) (Chemical formula 6)

[Chemical 6] [However, in the general formula (III), R ¹ has the same meaning as in the general formula (I), and n represents 1 or 2. ] It is obtained by a condensation reaction with a compound represented by

The compound of the general formula (II) can be synthesized, for example, by the following procedure. Optically active 2-O- (1-ethoxyethyl) carboxylic acid dimethylamide was treated with 4-tert-butoxyphenyl magnesium bromide to give 1- (1-ethoxyethoxy) alkyl [4- (tert-butyloxymethyl) phenyl. ] Ketone is converted to acetal to obtain an acetal of (1-hydroxy) alkyl [4- (tertiarybutyloxymethyl) phenyl] ketone, a hydroxyl group is sulfonated, and asymmetric rearrangement reaction and transesterification reaction are performed. Go 4-
(1-Alkoxycarbonyl) alkylbenzyl alcohol is obtained, which is oxidized with active manganese dioxide to give 4-
(1-Hexyloxycarbonyl) alkylbenzaldehyde and further oxidized with Jones reagent.

[Chemical 7]

Specific compounds of the general formula (II) include, for example, the following compounds. (S) -4- [1-
(Methoxycarbonyl) alkyl] benzoate,
(S) -4- [1- (ethoxycarbonyl) alkyl]
Benzoate, (S) -4- [1- (propoxycarbonyl) alkyl] benzoate, (S) -4- [1-
(Buxycarbonyl) alkyl] benzoate, (S)
-4- [1- (pentoxycarbonyl) alkyl] benzoate, (S) -4- [1- (hexoxycarbonyl) alkyl] benzoate, (S) -4- [1- (heptoxycarbonyl) alkyl] benzoate , (S)
-4- [1- (octoxycarbonyl) alkyl] benzoate, (S) -4- [1- (nonoxycarbonyl)
Alkyl] benzoate, (S) -4- [1- (decyloxycarbonyl) alkyl] benzoate, (S) -4
-[1- (undecyloxycarbonyl) alkyl] benzoate, (S) -4- [1- (dodecyloxycarbonyl) alkyl] benzoate, (S) -4- [1- (tridecyloxycarbonyl) alkyl] benzoate,
(S) -4- [1- (Tetradecyloxycarbonyl) alkyl] benzoate, (S) -4- [1- (Pentadecyloxycarbonyl) alkyl] benzoate, (S)
-4- [1- (hexadecyloxycarbonyl) alkyl] benzoate, (S) -4- [1- (heptadecyloxycarbonyl) alkyl] benzoate, (S) -4
-[1- (octadecyloxycarbonyl) alkyl] benzoate, (S) -4- [1- (nonadecyloxycarbonyl) alkyl] benzoate, (S) -4- [1-
(Eicosanoxycarbonyl) alkyl] benzoate, and optical isomers thereof (R form). Here,
Alkyl is an alkyl group having 1 to 10 carbon atoms, that is, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
It is a decyl group or a branched isomer group thereof.

The compound of the general formula (III) is a known substance and can be produced by alkylating 4- (4-hydroxyphenyl) phenol.

The condensation reaction between the compound of the general formula (II) and the compound of the general formula (III) is carried out when the compound X of the general formula (II) is a hydroxyl group. II
Almost equivalent amount of the compound of I) is taken, and halogen type solvent such as methylene chloride and chloroform, ether type solvent such as diethyl ether and tetrahydrofuran, aromatic hydrocarbon type solvent such as benzene and toluene, or alkane type solvent such as hexane and heptane. In the halogen solvent such as methylene chloride or chloroform, in the presence of a catalyst such as 4-dimethylaminopyridine, dicyclohexylcarbodiimide, diisopropylcarbodiimide or the like is added in an appropriate amount, preferably 1 equivalent or more, at an appropriate temperature, It is preferably carried out with stirring at a temperature not higher than the reflux temperature of the solvent used.

When X is halogen, there are two methods. The first method is the compound of general formula (II)
Almost equivalent amount of the compound of I) is taken in a solvent of a base such as pyridine or triethylamine, or a solvent containing 1 equivalent or more of these bases (a halogen solvent such as methylene chloride or chloroform, an ether solvent such as diethyl ether or tetrahydrofuran, Aromatic hydrocarbon solvent such as benzene or toluene, or alkane solvent such as hexane or heptane), preferably in methylene chloride or chloroform containing 1 equivalent or more of a basic amine such as pyridine or triethylamine, at room temperature or lower, preferably Stir under ice cooling.

In the second method, the phenol derivative of the general formula (III) is treated with one or more equivalents of a metal salt forming agent such as sodium hydride, lithium diisopropylamide, butyllithium to form a phenol metal salt, Ether solvents such as diethyl ether and tetrahydrofuran,
The reaction is carried out in an aromatic hydrocarbon solvent such as benzene or toluene or an alkane solvent such as hexane or heptane at room temperature or lower, preferably under ice cooling, together with the compound of the general formula (II) with stirring.

After the reaction, thin layer chromatography using an adsorbent such as silica gel, column chromatography,
The compound of the general formula (I) is recovered using a conventional purification method such as recrystallization. At this time, the pH of the liquid is 10 or more basic,
Alternatively, avoid acidity of 5 or less, and avoid high temperature of 50 ° C or more.

[0019]

EXAMPLES Examples of the present invention will be shown below. Example 1 4-octoxyphenyl (S) -4- [1
Synthesis of-(butoxycarbonyl) ethyl] benzoate

[Chemical 8]

(S) -4- [1- (Butoxycarbonyl) ethyl] benzoic acid 11.9 mg (0.0)
48 mmol, 1.0 equivalent) was dissolved in 2 ml of methylene chloride and 4-octoxyphenol 13.4 mg (1.1 times equivalent), 1,3-diisopropylcarbodiimide 22.4.
μl (2 equivalents), N, N-dimethylaminopyridine 1.
2 mg (0.2 times equivalent) was added and the mixture was refluxed. After 6 hours, 22.4 μl of 1,3-diisopropylcarbodiimide was added, and the mixture was refluxed for 6 hours. The oily residue obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel thin layer chromatography (developing solvent: hexane / chloroform / diethyl ether = 5).
/ 1/1, volume ratio), 4-octoxyphenyl (S) -4- [1- (butoxycarbonyl) ethyl]
12.7 mg (59% yield) of benzoate was obtained as a white solid.

The physicochemical properties of the obtained white solid are as follows. (1) Specific rotation [α] _D ²⁶ : 13.4 ° (c 0.17, C
HCl ₃ ) (2) Infrared absorption spectrum: ν (cm ^-1 ) 2960, 2932, 2876, 2860, 1738,
16121598, 1552, 1506, 1472, 1
420, 1394, 1376, 1312, 1274, 1
246, 1196, 1178, 1122, 1102, 1
076, 1018, 962, 936, 904, 872,
860, 822, 800, 782, 770, 746, 7
24, 700, 634, 574, 546, 524 (3) Nuclear magnetic resonance spectrum: δ (ppm) 0.89 (t × 2, 3H × 2, CH ₂ CH ₃ , J = 7.3H)
z), 1.1 to 1.7 [m, 14H, OCH ₂ CH ₂ CH _{2
CH 3, OCH 2 CH 2 (} C H 2) 6 CH 3], 1.54
(D, 3H, CHCH ₃ , J = 7.2Hz), 1.79
_{(Q, 2H, OCH 2 C} H 2 CH 2 CH 3, J = 6.6H
z), 3.81 (q, 1H, C H Me, J = 7.2H)
z), 3.96 (t, 2H , C 6 H 4 -OC H 2, J = 6.
5 Hz), 4.09 (t, 2H, COOC H ₂ , J = 6.
6Hz), 6.92 (d, 2H , C 6 H 4, J = 9.0H
z), 7.10 (d, 2H , C 6 H 4 J = 9.0Hz),
_{7.44 (d, 2H, C 6} H 4, J = 8.3Hz), 8.1
5 (d, 2H, C ₆ H ₄ , J = 8.3 Hz) In the above-mentioned nuclear magnetic resonance spectrum, the parentheses indicate the type of peak and the integrated intensity ratio, and if J is present, it indicates the binding constant. . Further, s means a singlet, d means a doublet, t means a triplet, q means a quintet, and m means a multiplet. The same applies to the following.

Example 2 Synthesis of 4- (4-octoxy) biphenyl (S) -4- [1- (propoxycarbonyl) ethyl] benzoate (Chemical Formula 9)

[Chemical 9]

(S) -4- [1- (propoxycarbonyl) ethyl] benzoic acid 20.7 mg (0.0
60 mmol) was dissolved in 2 ml of methylene chloride, and 4-
(4-octoxy) biphenol 28.8 mg (1.1 times equivalent) 1,3-diisopropylcarbodiimide 22.1
μl (2.0 times equivalent) and N, N-dimethylaminopyridine 1.1 mg (0.1 times equivalent) were added and the mixture was refluxed for 5 hours. The oily residue obtained by concentrating the reaction solution under reduced pressure was purified by silica gel thin layer chromatography (hexane / chloroform / diethyl ether = 15/2/3) to give 4- (4-octoxy) biphenyl (S) -4-. [1- (propoxycarbonyl) ethyl] benzoate 28.6 mg (yield 63
%) As a white solid. (1) Specific rotation [α] _D ²³ : 15.8 ° (c 0.47, C
HCI ₃ ) (2) Infrared absorption spectrum: ν (cm ^-1 ) 2932, 2856, 1742, 1610, 1574,
1502, 1470, 1420, 1392, 1380,
1338, 1276, 1266, 1222, 1202,
1168, 1120, 1080, 1020, 1000,
962, 942, 902, 876, 856, 836, 8
04, 772, 760, 744, 726, 698, 64
4, 516 (3) Nuclear magnetic resonance spectrum: δ (ppm) 0.88 (t, 6H, CH ₂ CH ₃ , J = 7.2 Hz),
1.1~1.7 [m, 14H, (C H 2) 7 CH 3], 1.5
5 (d, 3H, C H -CH 3, J = 7.2Hz), 1.8
_{1 (m, 2H, COOCH 2} C H 2 CH 3, J = 8.3H
z), 3.83 (q, 1H, CHMe, J = 7.2H)
z), 4.00 (t, 2H , C 6 H 4 -OCH 2, J = 6.
5 Hz), 4.06 (t, 2H, COOCH ₂ , J = 6.
6Hz), 6.97 (d, 2H , C 6 H 4, J = 7.5H
z), 7.24 (d, 2H, C ₆ H ₄ ), 7.47 (d, 2
_{H, C 6 H 4),} 7.50 (d, 2H, C 6 H 4), 7.59
(D, 2H, C ₆ H ₄ , J = 7.3 Hz), 8.18 (d,
_{2H, C 6 H 4, J} = 7.4Hz)

Example 3 Synthesis of 4- (4'-octoxy) biphenyl (S) -4- [1- (butoxycarbonyl) ethyl] benzoate (Chemical Formula 10)

[Chemical 10]

(S) -4- [1- (butoxycarbonyl) ethyl] benzoic acid 15.0 mg (0.0)
60 mmol, 1.0 eq) was dissolved in 2 ml of methylene chloride to give 4- (4'-octoxy) biphenol 19.8.
mg (1.1 times equivalent), 1,3-diisopropylcarbodiimide 14.1 μl (1.5 times equivalent) and N, N-dimethylaminopyridine 0.7 mg (0.1 times equivalent) were added, and the mixture was refluxed for 5 hours. . Rf = 0.76 (main spot) by silica gel thin layer chromatography (developing solvent: chloroform)
After confirming the formation of the desired product, the reaction solution was concentrated under reduced pressure to obtain an oily residue. This was purified by silica gel thin layer chromatography (developing solvent: hexane / chloroform / diethyl ether = 15/2/3, volume ratio), and 4- (4′-
Octoxy) biphenyl (S) -4- [1- (butoxycarbonyl) ethyl] benzoate (18.7 mg, 59% yield) was obtained as a white solid.

The physicochemical properties of the obtained white solid are as follows. (1) Specific rotation [α] _D ²⁷ : 8.0 ° (c 0.37, CH
Cl ₃ ) (2) Infrared absorption spectrum: ν (cm ⁻¹ ) 2960, 2936, 2860, 1744, 1610,
1502, 1470, 1418, 1390, 1378,
1324, 1274, 1224, 1206, 1168,
1132, 1120, 1080, 1020, 1000,
962, 940, 876, 856, 836, 806, 7
70, 746, 726, 698, 516 (3) Nuclear magnetic resonance spectrum: δ (ppm) 0.89 (t, 6H, CH ₂ CH ₃ , J = 7.2 Hz),
1.1~1.7 [m, 14H, (C H 2) n CH 3], 1.5
5 (d, 3H, CH- C H 3, J = 7.2Hz), 1.8
_{1 (q, 2H, COOCH 2} C H 2 CH 2, J = 8.3H
z), 3.82 (q, 1H , C H Me, J = 7.2H
z), 4.00 (t, 2H , C 6 H 4 -OC H 2, J = 6.
5 Hz), 4.09 (t, 2H, COOC H ₂ , J = 6.
6Hz), 6.97 (d, 2H , C 6 H 4, J = 8.7H
z), 7.24 (d, 2H, C ₆ H ₄ ), 7.46 (d, 2
H, C ₆ H ₄ , J = 8.3 Hz, 7.51 (d, 2H, C
₆ H ₄ , J = 8.6 Hz, 7.59 (d, 2 H, C ₆ H ₄ ,
J = 8.5 Hz), 8.18 (d, 2H, C ₆ H ₄ , J =
8.2 Hz)

Example 4 4- (4'-octoxy) biphenyl (S) -4- [1- (hexoxycarbonyl)
Synthesis of ethyl] benzoate

[Chemical 11]

(S) -4- [1- (hexoxycarbonyl) ethyl] benzoic acid 17.2 mg (0.0)
62 mmol, 1.0 equiv.) Was dissolved in 2 ml of methylene chloride to give 4- (4'-octoxy) biphenol 20.3.
mg (1.1 equivalent), 1,3-diisopropylcarbodiimide 14.5 μl (1.5 equivalent) and N, N-dimethylaminopyridine 0.8 mg (0.1 equivalent) were added and the mixture was refluxed. After 3 hours, 4.8 μl (0.5 times equivalent) of 1,3-diisopropylcarbodiimide was added, and the mixture was refluxed for 2 hours. After confirming the formation of the desired product at Rf = 0.55 (main spot) by silica gel thin layer chromatography (developing solvent: methylene chloride), the reaction solution was dissolved in 10 ml of ethyl acetate, 10 ml of 0.1M hydrochloric acid, and then distilled water. It was washed with 10 ml and dried over magnesium sulfate. The organic layer was concentrated under reduced pressure to obtain an oily residue. This was purified by silica gel thin layer chromatography (developing solvent: methylene chloride), and
-(4'-Octoxy) biphenyl (S) -4- [1
-(Hexoxycarbonyl) ethyl] benzoate 2
0.4 mg (59% yield) of white solid was obtained.

The physicochemical properties of the obtained white solid are as follows. (1) Specific rotation [α] _D ²⁶ : 11.2 ° (c 0.18,
CHCl ₃ ) (2) Infrared absorption spectrum: ν (cm ⁻¹ ) 2960, 2936, 2860, 1736, 1612,
1574, 1558, 1500, 1476, 1420,
1396, 1376, 1322, 1310, 1276,
1252, 1210, 1170, 1122, 1086,
1044, 1016, 1000, 960, 916, 87
8, 860, 836, 810, 774, 746, 72
2, 698, 664, 634, 548, 536, 51
2,480 (3) Nuclear magnetic resonance spectrum: δ (ppm) 0.86 (t, 3H, CH ₂ CH ₃ , J = 6.8 Hz),
0.94 (t, 3H, CH ₂ CH ₃ ), 1.1 to 1.7
[M, 18H, (C H 2) n CH 3], 1.55 (d, 3
_{H, CH-C H 3,} J = 7.2Hz), 1.81 (m, 2
_{H, COOCH 2 C H 2 CH} 2), 3.82 (q, 1H, C
H Me, J = 7.2 Hz), 4.00 (t, 2H, C ₆ H _{4
-OC H 2, J = 6.7Hz)} , 4.08 (t, 2H, C
OOC H ₂ , J = 6.7 Hz), 6.98 (d, 2H, C ₆
H ₄ , J = 11.6 Hz), 7.3 (d × 2, 2H × 2,
_{C 6 H 4), 7.46 (} d, 2H, C 6 H 4, J = 8.3H
z), 7.51 (d, 2H , C 6 H 4, J = 8.7Hz),
_{7.59 (d, 2H, C 6} H 4, J = 8.7Hz), 8.1
_{8 (d, 2H, C 6} H 4, J = 8.3Hz)

Example 5 4- (4'-octoxy) biphenyl (S) -4- [1- (octoxycarbonyl)
Synthesis of ethyl] benzoate

[Chemical 12]

(S) -4- [1- (Hectoxycarbonyl) ethyl] benzoic acid 13.1 mg (0.0
43 mmol, 1.0 eq) was dissolved in 2 ml of methylene chloride to give 4- (4'-octoxy) biphenol 14.0.
mg (1.1 equivalent), 1,3-diisopropylcarbodiimide 10.0 μl (1.5 equivalent) and N, N-dimethylaminopyridine 0.8 mg (0.1 equivalent) were added and the mixture was refluxed. After 3 hours, 10.0 μl of 1,3-diisopropylcarbodiimide was added, and the mixture was refluxed for 4 hours. Silica gel thin layer chromatography (developing solvent: hexane / chloroform / diethyl ether = 5/1/1, volume ratio) confirmed the formation of the target product at Rf = 0.55 (main spot), and concentrated the reaction solution under reduced pressure. An oily residue was obtained. This was purified by silica gel thin layer chromatography (developing solvent: hexane / chloroform / diethyl ether = 5/1/1, volume ratio), and 4- (4′-octoxy) biphenyl (S) -4- [1- ( Octoxycarbonyl) ethyl] benzoate (8.2 mg, 33% yield) was obtained as a white solid.

The physicochemical properties of the obtained white solid are as follows. (1) Specific rotation [α] _D ²⁶ : 9.1 ° (c0.16, CHC
13) (2) Infrared absorption spectrum: ν (cm ⁻¹ ) 2960, 2932, 2860, 1734, 1612,
1576, 1558, 1500, 1470, 1456,
1420, 1392, 1374, 1332, 1274,
1250, 1206, 1180, 1116, 1078,
1016, 1002, 956, 882, 858, 83
8, 804, 774, 754, 722, 702, 63
4, 554, 524 (3) Nuclear magnetic resonance spectrum: δ (ppm) 0.7 to 1.1 (t × 2, 3H × 2, CH ₂ CH ₃ ), 1.
1~1.9 [m, 15H, CH- C H 3, OCH 2 (C
_{H 2) 6 CH 3],} 3.82 (q, 1H, C H Me, J =
7.1Hz), 4.00 (t, 2H , C 6 H 4 -OC H 2,
J = 6.5 Hz), 4.08 (t, 2H, COOC H ₂ ,
J = 6.7 Hz), 6.97 (d, 2H, C ₆ H ₄ , J =
8.6Hz), 7.2 (d, 2H , C 6 H 4), 7.46
_{(D, 2H, C 6 H} 4, J = 8.3Hz), 7.51 (d,
2H, C ₆ H ₄ , J = 8.6Hz, 7.59 (d, 2H, C ₆ H ₄ , J = 8.5Hz), 8.18 (d, 2)
H, C ₆ H ₄ , J = 8.3Hz)

Example 6 Utilization as Liquid Crystal Compound The compounds obtained in Examples 1 to 5 were heated to about 120 ° C. to form an isotropic liquid, and this was a polyimide alignment film (PQ1800 manufactured by Hitachi Chemical Co., Ltd., film thickness 200). ± 20Å) is formed,
The cell for evaluation was assembled using a spacer having a thickness of 2 μm so that the rubbing directions were parallel to each other, and the cell was gradually cooled and oriented. Phase change observed with a polarizing microscope, and ±
Table 1 shows the response time and spontaneous polarization measured at 65 ° C. by applying an electric field of 5 V / μm. In Table 1, the numbers indicate temperatures (° C.), C is a crystalline phase, S _X1 , S _X2 , and S _X3 are higher order smectic phases with unknown attributes, S _A is a smectic A phase, and N is N.
* Chiral nematic phase, I means isotropic phase, respectively.

[Table 1]

[0034]

The optically active aromatic group-substituted alkanoic acid ester derivative of claim 1 is a novel compound. This compound exhibits an S _C * phase in a wide temperature range including room temperature, and is useful as a material for a ferroelectric liquid crystal display. According to the production method of claim 2, the optically active aromatic group-substituted alkanoic acid ester derivative of claim 1 can be produced.

Claims (2)

[Claims] 1. General formula (I) (Chemical formula 1) [In the general formula (I), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents an alkyl group having 1 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms or Represents an alkoxyalkyl group, n represents 1 or 2, and C * represents an asymmetric carbon atom. ] An optically active aromatic group-substituted alkanoic acid ester derivative represented by: 2. General formula (II) (Chemical formula 2) [Wherein, in the general formula (II), R ² represents an alkyl group having 1 to 10 carbon atoms, R ³ represents an alkyl group or an alkoxyalkyl group having 1 to 20 carbon atoms, X represents a hydroxyl group or halogen, C * represents an asymmetric carbon atom. ] And a compound represented by the general formula (III) (Chemical Formula 3): [However, in the general formula (III), R ¹ represents an alkyl group,
n represents 1 or 2. ] The manufacturing method of the aromatic-group substituted alkanoic acid ester derivative of Claim 1 which makes it react with the compound represented by these.