JPH06116196A - Optically active compound - Google Patents

Abstract

PURPOSE:To provide a new optically active compound consisting of an aromatic compound containing fluorine-containing alkyl group, having high stability, capable of inducing large spontaneous polarization, effective as a component for a liquid crystal composition exhibiting improved electric field response and useful for various optical elements, etc. CONSTITUTION:The objective compound of formula V (X2 is OCH2 or OOC) [e.g. 3-(4-hexyloxyphenyl)-4,4,4-trifluorobutanoic acid 4-(5-decylpyrimidin-2-yl) phenyl ester] is produced by reacting an optically active 3-(4- hydroxyphenyl)-4,4,4-trifluorobutanoic acid with hexyl iodide, etc., in dimethylformamide in the presence of sodium hydride, treating the obtained compound of formula I (R2 is 1-18C alkyl) with thionyl chloride to obtain an acid chloride derivative and reacting the derivative with a compound of formula II [R1 is same as R2; X1 is single bond, O, CO, COO, etc.; A1 to A3 are group of formula III (Y1 and Y2 are H or halogen), formula IV, etc.; (m) and (n) are 0 or 1].

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel optically active compound,
Particularly, it relates to an optically active compound which is useful as a component of a liquid crystal composition used in a liquid crystal element.

[0002]

2. Description of the Related Art Conventionally, as various optical elements characterized by having optical activity, many are known as exemplified below.

1) Utilizing the cholesteric / nematic phase transition effect in the liquid crystal state [J.J.
Wisoki, A Adams, W Hars "Physics Review Letters" (JJ Wysok
i, A. Adams and W. Haas; Phys.
Rev. Lett. ) 20, 1024 (1968)],

2) Utilizing the white Taylor type guest-host effect in the liquid crystal state [DL White, GM Tailor "Journal of
Applied Physics "(DL White a
nd G.n. N. Taylor; J. Appl. Phy
s. ), 45 , 4718 (1974)],

3) Utilizing the ferroelectric effect of chiral smectic C phase, H phase, F phase, I phase, G phase, K phase, and J phase in the liquid crystal state [NA Clark, Estella Gawell "Applied Physics Letters "(NA Clarkand S.T.Lage
rwall; Appl. Phys. Lett. ), 3
6 , 899 (1980)],

4) By fixing a substance having a cholesteric phase in a liquid crystal state in a matrix, by utilizing its selective scattering property, it is used as a notch filter or a bandpass filter [FJ Kern "Applied Physics Letters" ( F.J.Ka
hn; Appl. Phys. Lett. ), 18, 23
1 (1971)], which is used as a circularly polarized beam splitter utilizing circular polarization characteristics [SD Jacobs, SD Jacobs,
SPIE), 37, 98 (1981)]; etc.

A detailed description of each method is omitted, but all are important as a display element or a modulation element.

An optically active compound is used as a main component of a functional material constituting these optical elements or as an important functional component although it is a relatively small amount component.
For example, Etch Arnold “Zeit Schrift
Fua Fuiji Kalish Chemie "(H. Arnol
d, Z. Phys. Chem. ), 226 , 146 (1
964), it is possible to control the kind and temperature range of a liquid crystal phase that appears in a liquid crystal state by adding another optically active substance or a liquid crystal compound to the above-mentioned optical element material, particularly a liquid crystal material. It is disclosed. Also,
It is expected that a compound having a large dipole will be introduced into a liquid crystal material driven by electric field response to obtain a liquid crystal material having a better electric field response. Many of such functional materials are synthesized from intermediates that are themselves optically active.

Further, among the optical elements characterized by having optical activity, in the method using the electric field response optical effect in the liquid crystal state, a polar group has been introduced in order to enhance the response. In particular, in a ferroelectric liquid crystal, the response speed is known to be proportional to the spontaneous polarization, and it is desired to increase the spontaneous polarization in order to increase the speed. From such a point, the peaker (P. Ke
Ller et al. have shown that the introduction of a chlorine group into an asymmetric carbon can increase spontaneous polarization and increase the response speed [SR Academy Science (C.
R. Acad. Sc. Paris), 282 C, 63
9 (1976)].

However, since the chlorine group introduced into the asymmetric carbon has the drawback of being chemically unstable, its improvement is desired.

[0011]

The present invention has been made in view of the above circumstances, and its main object is to provide an optically active compound having a trifluoromethyl group at the asymmetric center. . More specifically, the present invention suppresses the free rotation of the dipole by introducing a trifluoromethyl group having a large dipole moment and a relatively bulky phenyl group directly into the asymmetric center, thereby suppressing the dipole. An object of the present invention is to provide an optically active compound effective as a component of a liquid crystal composition that induces large spontaneous polarization by orienting in a fixed direction and exhibits a better electric field response.

[0012]

That is, the present invention provides the following general formula (I):

[0013]

[Chemical 5]

(In the formula, R ₁ and R ₂ are each 1 to 1 carbon atoms.
18 straight-chain or branched alkyl groups are shown. X ₁
Is a single bond, -O-, -CO-, -COO-, -OOC.
Represents-, and X ₂ represents -OCH _2- , -OOC-. A ₁ , A ₂ , and A ₃ are

[0015]

[Chemical 6] Indicates. Y ₁ and Y ₂ represent H or halogen.
m and n are 0 or 1. * Indicates that it is optically active. ) Is provided.

Of the optically active compounds represented by the above general formula (I), the compound in which X ₂ is —OCH ₂ — is preferable.

Among the optically active compounds represented by the above general formula (I), particularly preferred compounds include the following (Ia) to (Ih).

[0018]

[Chemical 7]

(In the formula, R ₁ and R ₂ are each 1 to 1 carbon atoms.
18 straight-chain or branched alkyl groups are shown. X ₁
Is a single bond, -O-, -CO-, -COO-, -OOC-
Indicates. Y ₁ and Y ₂ represent H or halogen. *
Indicates that it is optically active. ) Further, more preferable compounds among the optically active compounds represented by the general formula (I) include the following (Ica) to (Ifb).

[0020]

[Chemical 8]

(In the formula, R ₁ and R ₂ are each 1 to 1 carbon atoms.
18 straight-chain or branched alkyl groups are shown. * Indicates that it is optically active. )

Further, R ₁ and R _{2 in the} general formula (I) are
Is preferably a linear alkyl group having 3 to 12 carbon atoms.

Next, a general method for synthesizing the optically active compound represented by the general formula (I) will be shown.

[0024]

[Chemical 9]

The optically active compound represented by formula (I) is preferably applied by the present applicant (Japanese Patent Application No.
No. 57260) and the following general formula (II)
Of the optically active 4,4,4-trifluoro-3- (4-hydroxyphenyl) butanoic acid alkyl ester.

[0026]

[Chemical 10] (In the formula, R represents a linear or branched alkyl group having 1 to 18 carbon atoms.)

Next, specific examples of the optically active compound represented by the general formula (I) will be shown below.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

[0046]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Optically active 3- (4-hexyloxyphenyl) -4,
Production of 4- (5-decylpyrimidin-2-yl) phenyl 4,4-trifluorobutanoate (Exemplified Compound 106) Optically active 3- (4-hexyloxyphenyl) -4,4,4- according to the following steps Trifluorobutanoic acid 4- (5
-Decylpyrimidin-2-yl) phenyl was prepared.

[0048]

[Chemical 29]

Step 1) Production of Optically Active Hexyl 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutanoate 97 mg (2.4 mm) of sodium hydride was placed in an eggplant flask.
ol) and 3 ml of dry dimethylformamide (DMF) were added to it, and optically active 3- (4-hydroxyphenyl)
190 mg of -4,4,4-trifluorobutanoic acid (0.
81 mmol) and 4 ml of dry DMF were added.
Further, a mixed solution of 516 mg (2.4 mmol) of hexyl iodide and 2 ml of dry DMF was added, and the mixture was heated and stirred at 80 ° C for 75 minutes.

After completion of the reaction, DMF was distilled off under reduced pressure, diluted hydrochloric acid was added, and the mixture was extracted with ether. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and dried. After distilling off the solvent, the product was purified by thin layer chromatography to obtain 275 mg (0.684 mm) of the desired product.
ol) was obtained.

Yield 84% [α] _D ²³ -31.6 °, [α] ₄₃₅ ²³ -6
7.0 ° (c1.668, EtOH)

Step 2) Production of optically active 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutanoic acid Optically active 3- (4-hexyloxyphenyl) -4,4,4 was added to an eggplant flask. -Hexyl trifluorobutanoate 2
75 mg (0.684 mmol) and 99% ethanol 2
ml, potassium hydroxide 90 mg, and water 1 ml were added, and the mixture was refluxed for 4 hours. After the reaction was completed, ether and water were added, and the mixture was extracted with an aqueous sodium hydroxide solution. Add hydrochloric acid to the extract to pH 1
And the released carboxylic acid was extracted with ether.

The extract thus obtained was washed with water, dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was distilled under reduced pressure to obtain 189 mg (0.594 mmol) of the desired product.

Yield 87%, b. p. 185 ° C / 0.3t
orr, [α] _D ²¹ −35.9 °, [α] ₄₃₅
²¹ −77.2 ° (c 0.912, CHCl ₃ ).

Step 3) Optically active 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutanoic acid 4-
Production of (5-decylpyrimidin-2-yl) phenyl 99 mg of optically active 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutanoic acid was added to a round bottom flask.
(0.31 mmol) and 4- (5-decylpyrimidine-
2-yl) phenol 98 mg (0.31 mmol),
Dimethylaminopyridine 19 mg (0.16 mmo
l) and 2 ml of dry dichloromethane were added, and the mixture was stirred at room temperature for 30 minutes.

192 mg (0.932 mmol) of dicyclohexylcarbodiimide (DCC) and 1 ml of dry dichloromethane were added thereto, and the mixture was further stirred at room temperature for 3 hours. After the reaction was completed, the crystals were removed by filtration. The filtrate was concentrated and purified by thin-layer column chromatography to obtain 162 mg (0.265 mmol) of the desired product.

Yield 85%, mp. 46 ° C. [α] _D ²⁴ −78.7 °, [α] ₄₃₅ ²⁴ −1
84 ° (c 0.715, CHCl ₃ )

Example 2 Optically active 1,1,1-trifluoro-2- (4-hexyloxyphenyl) -4- {4- (5-decylpyrimidin-2-yl) phenoxy} butane (Exemplified Compound 5
3) Production of optically active 1,1,1-trifluoro-
2- (4-hexyloxyphenyl) -4- {4- (5
-Decylpyrimidin-2-yl) phenoxy} butane was prepared.

[0059]

[Chemical 30]

Step 1) Production of Optically Active 3- (4-Hexyloxyphenyl) -4,4,4-trifluorobutanol Lithium aluminum hydride 82 was placed in an eggplant flask.
mg (2.15 mmol) and dry ether were added. In addition, optically active 3- (4-hexyloxyphenyl)-
Hexyl 4,4,4-trifluorobutanoate 288 mg
A mixture of (0.716 mmol) and 4 ml of dry ether was added dropwise. After heating under reflux for 4 hours, diluted hydrochloric acid was added, and the mixture was extracted with ether. After adding anhydrous sodium sulfate and drying, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain the desired product 208 mg.
(0.684 mmol) was obtained.

Yield 96%, bp 135 ° C./0.15
torr [α] _D ²⁷ + 45.3 °, [α] ₄₃₅ ²⁶ +9
2.4 ° (c 0.900, CHCl ₃ )

Step 2) Production of Optically Active 4-Toluenesulfonic Acid 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutyl 4-Toluenesulfonic acid chloride 137 was placed in a round bottom flask.
mg and dry dichloromethane 1 ml are added, and the optical activity is 3-
(4-Hexyloxyphenyl) -4,4,4-trifluorobutanol 208 mg and dry dichloromethane 2 m
l mixed solution was added, and further triethylenediamine 80 mg
A mixture of (0.714 mmol) and 1 ml of dry dichloromethane was added. Stir in an ice bath for 24 hours. After the reaction was completed, dilute hydrochloric acid was added, and the mixture was extracted with ether. After anhydrous sodium sulfate was added and dried, the solvent was distilled off, and purification by thin layer chromatography was carried out to obtain 247 mg of the desired product (0.53
9 mmol) was obtained.

Yield 79% [α] _D ²³ -40.5 °, [α] ₄₃₅ ²³ +8
1.7 ° (c 0.878, CHCl ₃ ).

Step 3) Optically active 1,1,1-trifluoro-2- (4-hexyloxyphenyl) -4- {4-
Preparation of (5-decylpyrimidin-2-yl) phenoxy} butane 60% -sodium hydride 13 mg in an eggplant flask.
(0.33 mmol) and 1 ml of dry DMF were added, to which was added a mixed solution of 82 mg (0.263 mmol) of 4- (5-decylpyrimidin-2-yl) phenol and 2 ml of dry DMF, and the mixture was stirred at room temperature for 10 minutes. Optically active 4-toluenesulfonic acid 3- (4-hexyloxyphenyl) -4,4,4-trifluorobutyl 120 mg
A mixed solution of (0.262 mmol) and 2 ml of dry DMF was added, and the mixture was stirred at room temperature for 6 hours and at 50 ° C. for 1 hour. After completion of the reaction, DMF was distilled off under reduced pressure, diluted hydrochloric acid was added, and the mixture was extracted with ether. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and dried. After the solvent was distilled off, purification was carried out by thin layer chromatography to obtain 141 mg (0.235 mmol) of the desired product.

Yield 90%, mp. 56 ° C [α] _D ²⁹ + 112 °, [α] ₄₃₅ ²⁸ +26
5 ° (c 0.702, CHCl ₃ )

Example 3 Optically active 1,1,1-trifluoro-2- (4-hexyloxyphenyl) -4- {4- (5-decyloxypyrimidin-2-yl) phenoxy} butane (Exemplified Compound 54 ) The optically active 1,1,1-trifluoro-2 (4-hexyloxyphenyl) -4- {4- (5
-Decyloxypyrimidin-2-yl) phenoxy} butane was prepared.

[0067]

[Chemical 31]

60% sodium hydride in eggplant flask
3 mg (0.33 mmol) and 1 ml of dry DMF were added, and a mixed solution of 85 mg (0.259 mmol) of 4- (5-decyloxypyrimidin-2-yl) phenol and 2 ml of dry DMF was added thereto, and the mixture was stirred at room temperature for 10 minutes. In addition, optically active 4-toluenesulfonic acid 3- (4-
Hexyloxyphenyl) -4,4,4-trifluorobutyl 119 mg (0.260 mmol) and dry DMF
2 ml of the mixed solution was added, and the mixture was stirred in a greenhouse for 6 hours and at 50 ° C. for 1 hour. After completion of the reaction, DMF was distilled off under reduced pressure, diluted hydrochloric acid was added, and the mixture was extracted with ether. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and dried.

After distilling off the solvent, the residue was purified by thin layer chromatography to obtain 139 mg (0.226 mmol) of the desired product.
Got

Yield 87% [α] _D ²⁷ + 111 °, [α] ₄₃₅ ²⁶ +26
0 ° (c 0.636, CHCl ₃ ) Phase transition temperature (° C.)

[0071]

[Equation 1]

Example 4 In 95 parts by weight of MORA8 having the structure shown below, 1,1,
1-trifluoro-2- (4-pentyloxy) phenyl-4- {4- (4-octylphenyl) phenoxy}
5 parts by weight of butane (Exemplary Compound 15) was added to obtain a liquid crystal composition.

[0073]

[Chemical 32]

This liquid crystal composition exhibits the SmC ^* phase,
Compared with MORA8 alone, spontaneous polarization is 2.5 times,
Response time is 22msec under the condition of ± 15V application and about 53
It became%.

[0075]

INDUSTRIAL APPLICABILITY According to the present invention, a novel optically active compound which is chemically stable can be provided. Since the trifluoromethyl group having a large dipole moment is directly connected to the asymmetric center, the optically active compound of the present invention may have a large spontaneous polarization when the compound itself has a ferroelectric phase. Be expected.

The optically active compound of the present invention is also effective as a material for imparting spontaneous polarization, and when added to a liquid crystal composition having a non-chiral smectic phase or a chiral smectic phase, spontaneous polarization is increased and a response is obtained. A liquid crystal composition with improved speed can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 69/86 9279-4H 69/92 9279-4H 69/94 9279-4H C07D 239/34 8615- 4C C09K 19/20 7457-4H 19/30 7457-4H 19/34 7457-4H G02F 1/13 500

Claims (4)

[Claims] 1. An optically active compound represented by the following general formula (I). [Chemical 1] _(Wherein, R 1, _{R 2} is .X ₁ showing a straight-chain or branched alkyl group having 1 to 18 carbon atoms is a single bond,
Represents -O-, -CO-, -COO-, -OOC-, X
₂ -OCH ₂ -, - OOC- shows a. A ₁ , A
₂ , A ₃ is Indicates. Y ₁ and Y ₂ represent H or halogen.
m and n are 0 or 1. * Indicates that it is optically active. ) 2. The optically active compound according to claim 1, wherein X ₂ is —OCH ₂ — in the optically active compound represented by the general formula (I). 3. The optically active compound according to claim 1, wherein the optically active compound represented by the general formula (I) is any one of the following (Ia) to (Ih). [Chemical 3] (In the formula, R ₁ and R ₂ represent a linear or branched alkyl group having 1 to 18 carbon atoms. X ₁ is a single bond, −
O-, -CO-, -COO-, -OOC- are shown. Y ₁
, Y ₂ represents H or halogen. * Indicates that it is optically active. ) 4. The optically active compound according to claim 1, wherein the optically active compound represented by the general formula (I) is any of the following (Ica) to (Ifb). [Chemical 4] (In the formula, R ₁ and R ₂ represent a linear or branched alkyl group having 1 to 18 carbon atoms. * Represents optically active.)