JPH03123750A - Optically active liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:An optically active liquid crystal compound expressed by formula I (R* is 4-13C optically active alkyl having asymmetric carbon atom; R is 1-20C straight-chain alkyl; A is OCO or O; X is H or F; either of Y and Z is single bond and the other is CH2CH2). EXAMPLE:Optically active 4-alkyloxycarbonyl-4-[2-(4-alkoxyphenyl)ethyl]biphenyl expressed by formula II. USE:An optically active liquid crystal compound, useful as a display element or electrooptical element, excellent in stability, having a wide temperature range capable of exhibiting a chiral smectic C phase and sufficiently mixable with other smectic liquid crystal compounds. PREPARATION:A compound expressed by formula (G) is reacted with a compound expressed by formula (B) in the presence of a catalyst expressed by the formula (PPh3)2PdCl2-CuI (Ph is phenyl) in triethylamine to provide a compound expressed by formula (H), which is then substituted with hydrogen in the presence of a Pd/C catalyst to afford the compound expressed by formula Ia.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an optically active liquid crystal compound useful for dual display elements or electro-optical elements.

[Conventional technology]

In recent years, applied research has been actively conducted on ferroelectric liquid crystals because they are characterized by a faster response speed than conventional nematic liquid crystals.

Ferroelectricity is classified into chiral smectic C phase, which is classified based on the arrangement of nine molecules, chiral smectic! It is expressed in the chiral smectic F phase, chiral smectic C phase, and chiral smectic H phase (hereinafter abbreviated as Sc* phase, S phase, S,* phase, Sc* phase, and S++* phase, respectively), and is based on ferroelectricity. The response is the following formula [a]r = 77
/Pi e E [:a:] (in the formula, τ is the response time, η is the viscosity of the liquid crystal material, Ps is the spontaneous polarization, and E is the electric field), so theoretically it takes 1 μs.
It becomes possible to obtain a display element that can respond up to

On the other hand, ferroelectric liquid crystal display materials that are actually used are required to have many properties, and it is currently difficult to provide these properties to a single liquid crystal compound, so several types of liquid crystal compounds are mixed. Attempts have been made to obtain practical display materials.

[Problem to be solved by the invention]

Therefore, as a ferroelectric optically active liquid crystal compound, it is thermally, optically and chemically stable.

It is required that the temperature range in which the chiranumectic C phase is exhibited is wide and that it can be mixed with various liquid crystal compounds.

[Means to solve the problem]

As a result of intensive research from the above viewpoint, the present inventors discovered a liquid crystal compound that has excellent stability, exhibits a chiral smectic C phase over a wide temperature range, and mixes well with other smectic liquid crystal compounds. It's all over.

That is, the present invention is based on the general formula [I] (wherein - represents an optically active alkyl group having an asymmetric carbon atom having 4 to 13 carbon atoms, R represents a linear alkyl group having 1 to 20 carbon atoms, A is a group -0C- or a group -0-1, X is a hydrogen atom or a fluorine atom, Y and Z are a group -CH2CH2- when Y is a single bond, Y is a group CHzC
It is an optically active liquid crystalline compound represented by (Z represents a single bond when Hz-).

A typical example of the compound represented by the general formula [■] is a combination of A, Y, and 2 in the formula 2.

It can be divided into the following groups.

The method for producing the compound represented by the general formula [■] (in which r, R and X have the same meanings as above) will be described in detail below, and an optically active alcohol is used as one of the raw materials. Optically active alcohols can be obtained at low cost from the viewpoint of industrial versatility. For example, 1-methylbutanol, 2-methylbutanol, 3-methylpentanol, 4-methylhexanol, l-methylheptatool.

Salers used include 5-methylhebutano/L/, 6-methyloctatool, and 1-methylpropatool.

The outline of the method for producing the compound of the present invention is as follows.

H3 H3 H3 H3 [CD CD) HS [E] [F] H3 [A] CB, 1 [G] (H) [D] [D] [K] [K] [L] [F] CM) and Effects] The compound of the present invention is a novel liquid crystalline compound exhibiting the following actions and characteristics.

First, it does not have any groups that easily decompose even in a moisture-containing atmosphere, and it does not contain any groups that are isomerized by light, so it is very stable against moisture and light.

Next, many of the liquid crystalline compounds of the present invention exhibit smectic C phase over a wide temperature range even when used alone, and therefore have high utility value as liquid crystalline substances.

Furthermore, by mixing the compounds of the present invention or the compound of the present invention with existing compounds having a smectic C phase, the temperature range exhibiting the smectic C phase can be expanded to a wide range including room temperature.

〔Example〕

The present invention will be explained below by way of examples.

% in the examples indicates weight %.

Production Example 1 Synthesis of 4-alkoxyphenylacetylene [B] 4-Alkoxybromobenzene (or 4-alkoxy-3- )~olopromobenzene) 0.234 nool, 2-methyl-3
-Butyn-2-ol 29.57? (0,352m
o+), trifue: /L/hos74:/”
1.0Of (3,81 mmol), dichlorobis(triphenylphosphine)palladium 0.529
(0,730 mmol) and triethylamine 200
mt was charged, stirred and dissolved, and 160 μm of copper iodide was added.

After stirring at room temperature for 3 hours, the mixture was gradually heated to bring the internal temperature to 90°C over 30 minutes. The reaction was allowed to proceed at this temperature for 20 hours.

After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, ether/I/300mt was added to the residue, and the mixture was washed with water.
It was dried with anhydrous sodium sulfate. After filtration, the ether was distilled off, and the residue was subjected to silica gel column chromatography (2
00 mesh silica gel 400? , developing solvent: benzene) to obtain a primary compound [A] as an intermediate.

H3 Then 500 c equipped with stirrer, thermometer and distillation equipment
The above compound (A) was placed in a nitrogen stream in a three-roast colander of c.
58.4 mmol, anhydrous toluene 12 omt and sodium hydride (60% Nujol [IJ]) 310
(2) was added and stirred at room temperature for 30 minutes. Heat gradually,
It took 30 minutes to bring the internal temperature to 70°C. The reflux of acetone (a by-product) began to distill out together with renin, but the reaction continued with further heating until the distillation temperature reached the boiling point of toluene. During this time, it took 2 hours to distill out the mixture. The volume of the solvent was 60 ml. After the reaction was completed, the temperature was returned to room temperature, 100 ml of benzene was added thereto, washed with water, and dried over anhydrous sodium sulfate. After filtration, the organic solvent was distilled off, and the residue was subjected to silica gel column chromatography (200 ml). 4-alkoxyphenylacetylene [B] (X=H,
F) Got it. Its structure is based on IR and H-NMR)
Y&Yoshi confirmed.

The results are shown in Table 1.

ff Preparation Example 2 4-Furkyloxycarbonylphenyl CH30 Alkyl p-bromobenzoate 64 mrnol, 2-mecal-3- in a nitrogen stream was placed in a 500 cc three-row flask equipped with a stirrer, a thermometer and a reflux condenser.
Butyn-2-ol 5.91 f (70rnmol
) , ) Riphenylphosphine 270 ”? (1
,03mmol), dichlorohynu(triphenylphosphine)palladium 140■(0.20mmol+)
and 60 ml of triethylamine were added, stirred and dissolved, and 45 ml of copper iodide was added. After stirring at room temperature for 3 hours,
It took 30 minutes to bring the internal temperature to 80°C. The reaction was allowed to proceed at this temperature for 10 hours.

After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, ether/L/300 ml was added to the residue, washed with water, and dried over anhydrous sodium sulfate. After passing through the ocean, the RH product was distilled off using silica gel column chromatography (200 mesh silica gel/L'100r).

developing solvent; dichloromethane) to form the primary compound [C]
was obtained as an intermediate.

H3 Next, 300 C equipped with a stirrer, thermometer and distillation device.
The above compound [C:] was added in a nitrogen stream to a three-row flask of C.
57.8 mmo+, anhydrous toluene 120m and sodium hydride (60% Nujol dispersant) 200~
and stirred at room temperature for 30 minutes. Heat gradually.

It took 30 minutes to bring the internal temperature to 70°C. Acetone (by-product) begins to reflux and begins to distill out together with toluene, but
The reaction was continued by further heating until the distillation temperature reached the boiling point of toluene. This took 2 hours, and the distilled solvent amounted to 60%
It was ml. After the reaction is complete, return to room temperature and add benzene 10
0 mt was added thereto, washed with water, and dried over anhydrous sodium sulfate. After filtration, the organic solvent was completely distilled off, and the residue was subjected to silica gel column chromatography (200 mesh silica gel/L).
/100f, development strategy: benzene), and the 4-alkyloxycarbonylphenylacetylene structure was confirmed by IR and H-NMR spectra 2,b.

Production Example 3 Synthesis of 4-alkoxyphenylacetylene CF] The reaction was carried out under the same conditions as Production Example 2, except that 4-alkoxybromobenzene (64 mmol) was used instead of the alkyl root (64 mmol) in Production Example 2. 4-alkoxyphenylacetylene CF) was obtained. Its structure was confirmed by IR and 'H-NMR spectra.

The results are shown in Table 3.

Example 1 4-Furkyloxycarboni)L/-
4 - 100c equipped with stirrer, thermometer and reflux condenser
c, 4-alkyloxycarbonyl-4-promobiphenizLz (:G:) 3.46
mmol, 4-alkoxyphenylacetylene CBI (X=H, F) obtained in Production Example 1 3.56 mmo
+, triphenylphosphine 21.2 mV (
0.081mrno+), cyclobis(triphenylphosphine)palladium9. 5 WIg( 0
．． 014 mmol) and 20 ml of triethylamine were charged under a nitrogen atmosphere, stirred and dissolved, and 5 ml of copper iodide was added.

After stirring at room temperature for 3 hours, the mixture was heated slowly to bring the internal temperature to 80°C over 30 minutes. The reaction was allowed to proceed at this temperature for 8 hours. After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, and Nitea v5Q ml was added to the residue, washed with water, and dried over anhydrous sodium sulfate. After filtration, ether is distilled off,
The residue was subjected to silica gel column chromatography (20
0 mesh silica gel 50 f, development mK: Hensen/hexane = 1/1) to form the 9th order compound [H]
was obtained as an intermediate.

Next, 1.0 mmo+ of the above compound (H),
50 ml of 5% palladium-carbon catalyst and 15 ml of tetrahydrofuran were charged, and the mixture was replaced with hydrogen and allowed to react at room temperature for 2 hours. After the reaction is complete, the catalyst is separated, the solvent is distilled off under reduced pressure, and the residue is subjected to silica gel column chromatography (
It was isolated by applying 200 mesh of silica cake/l/2091 developing solvent: benzene). Further, it was recrystallized from hexane to form 4-alkyloxycarbonyl-sipheni/I/)ethyl]biphenylQa] (X=H,
F) was obtained in a yield of 50-95. Its structure was confirmed by IR and H-NMR spectra.

Example 1 [Compound level 17] Yield 85% IR: v KB'"" (Confucian-1) 2
924.171 2+ 160 8.

1512, 1112 "H-NMR: J'R' (ppm) 8.1 (2H.
d), 7.6 (2H.d).

7, 5 (2H, d), 7.4 - 6.7 (6H.
m).

4, 2 (2H, d), 3.9 (2H.t).

2, 9 (4H, S), 2.2 ~ 0.6 (28H.m)
Example 2 [Compound 25] Yield 73% IR: v KB'di"(1-')
2 924,17 0 4- 160 6+1516
, 1124 "H-NMR: δ'7B313 (ppm) 8.0 (
2H, d) + 7.6 (2H, d).

7, 5 (2H. d), 7.3-6.7 (5) 1.
m).

4, 1 (2H. d), 4.0 (2H,
t).

2,9 (4H,s), 2.1~0.6 (
28H, m) In a 100 cc three-roar flask equipped with a stirrer, a thermometer and a reflux condenser, the 4-
Alkyloxycarbonylphenylacetylene [D:l
3. 0mmo! , 4-alkoxy-4-bromobiphenyl 3,0 mmol, )riphenylphosphine 19.9■ (0.086ry+mol), dichlorobis(triphenylphosphine)palladium 8.
0.0 (0.011 mmol) and 20 ml of triethylamine were charged under a nitrogen atmosphere and dissolved with stirring.

5μ of copper iodide was added. After stirring at room temperature for 3 hours, the mixture was slowly heated to bring the internal temperature to 80° C. over 30 minutes.

The reaction was allowed to proceed at this temperature for 8 hours. After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, and the residue was diluted with ether 5.
Q ml was added thereto, washed with water, and dried over anhydrous sodium sulfate. After filtration, the ether was distilled off, and the residue was subjected to silica gel column chromatography (200 mesh silica gel/1
150g. Developing solvent: benzene/hexane = 1/l) to obtain the following compound [J] as an intermediate.

Next, the above compound (J:] 1.0 mm+
, 50 ml of 5% palladium-carbon catalyst and 15 ml of tetrahydrofuran were charged. The mixture was replaced with hydrogen and reacted at room temperature for 2 hours. After the reaction was completed, the catalyst was separated, the solvent was distilled off under reduced pressure, and the residue was isolated by silica gel column chromatography (200 mesh silica gel 202, developing solvent: benzene). Further, it was recrystallized from hexane to give 4-alkoxy-4-C2-C4-alkyloxypolonylphenyl/I/)ethyl]biphenyl (Ib).
Obtained with an overall yield of 80-90%. Its structure is IR and 'H
- Confirmed by NMR spectrum.

Example 3 [Compound N127) - Yield 80% IR Niji-, (m) 2924.17
12.1610.

1502, 1106 'H-NMR: δ? u%'3 (ppm) 8.1~7
．． 8 (2H, m).

7, 6-6.8 (10H, In).

5.4 to 4.9 (IH, m).

4.0 (2H, t), 3.0 (4H, s).

2.1-0.6 (35H, m) Compounds [Ia) and [Ib: obtained in Examples 1 and 2]
] Table 4 shows the phase change humidity temperature.

Example 3 4-Alkoxy-4-(obtained as 2-(4-amer).

(4-alkoxy-4-bromopyphenyl [:K)] 1. Ommo! , 4- obtained in Production Example 1
Alkoxyphenylacetylene 1,2 mmo! , triphenylphosphine10.
4 trq (0.040 mmol), dichlorobis(
triphenylphosphine) palladium 13.3* (
0.019 mmol) and triethylamine 20
ml under nitrogen atmosphere and stirred to dissolve.

5μ of copper iodide was added. After stirring at room temperature for 3 hours, the mixture was slowly cooled and heated to bring the internal temperature to 80° C. over 30 minutes.

The reaction was allowed to proceed at this temperature for 8 hours. After the reaction, the temperature was returned to room temperature, triethylamine was distilled off under reduced pressure, and the residue was diluted with ether 5.
0 ml was added thereto, washed with water, and dried over anhydrous sodium sulfate. After filtration, the ether was distilled off, and the residue was subjected to silica gel column chromatography (200 mesh silica gel/L).
/ 5Q t, developing solvent: benzene/hexane = 1/
4), then pour the following compound [L] into a flask equipped with a stirrer, a thermometer, and a rubber balloon filled with hydrogen gas.
The above compound (L': l 0.5 mmo+, 5% palladium-carbon catalyst 50 μ and tetrahydrofuran 15
ml was charged, the atmosphere was replaced with hydrogen, and the reaction was allowed to proceed at room temperature for 2 hours. After the reaction is complete, the catalyst is separated and the solvent is distilled off under reduced pressure.
The residue was subjected to silica gel column chromatography (200
It was isolated by using mesh silica gel 201 (developing solvent: benzene/hexane = 1/1). Further recrystallization from hexane yields 4-alkoxy-4-[2-(4-alkoxyphenyl/)ethyl]biphenyl/' [Ic]
(x = H, F) was obtained in a yield of 50-90%. Its structure was confirmed by IR and 1H-NMR spectroscopy.

Example 4 [Compound Na29] Yield 60% ■ R Niji KBr
diak(--1) 2956. 16081
1512.

1252, 816"H-NMR: J'5'3 (ppm) 7.6
~6.7 (12 Hl m).

4.1 to 3.7 (4H, m).

2, 9 (4H, a).

2, 2 ~ 0.7 (28 H. m) Example 5 [Compound height 31] Yield 9o% IR Niji'rirxdisk (,,, -1) 1H-N
MR: δS 13 (ppm) 2924, 1620. 1520.

22 7, 7 ~ 6.3 (11 H, m).

4, 1-3.7 (4H.m).

3, 9 (4H.S).

2, 1-0.5 (24H.m) xyphenylacetylene CF] 1.1 mmol, 4
-Alkoxy-4-promobiphenylene/L/1. 1 m
mol, ) Riphenylphosphine 21. 2 W
(0.081 mmol), dichlorohis (
triphenylphosphine) palladium 8.6”S' (
0. 012 mmol) and triethylamine 2
0 ml was charged under a nitrogen atmosphere, stirred and dissolved, and 5 ml of copper iodide was added. After stirring at room temperature for 3 hours, the mixture was gradually heated.

It took 30 minutes to bring the internal temperature to 80°C. The reaction was allowed to proceed at this temperature for 8 hours. After the reaction, the temperature was returned to room temperature, and triethylamine was distilled off under reduced pressure. 50 ml of ether was added to the residue, washed with water, and dried over anhydrous sodium sulfate. After filtration, the ether was distilled off, and the residue was purified by silica gel column chromatography. The mixture was subjected to lithography (200 mesh silicage #5Q f, developing solvent: benzene/hexane = 1/4) to obtain the following compound [M] as an intermediate.

100 cc with stirrer, thermometer and reflux condenser
Next, add the stirrer, thermometer, and hydrogen gaff to the 9th grade lower rack in production example 3.
:l Add the above compound (CM) to a flask equipped with a balloon.
1.0 mmo+.

5% palladium-carbon 50 cm and tetrahydrofuran 1
5 ml was charged, the atmosphere was replaced with hydrogen, and the reaction was allowed to proceed at room temperature for 2 hours. After the reaction, the catalyst was separated, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (20
0 mesh silicage) V2QJ developing solvent: benzene/
Hexane = 1/1) and isolated. Further, it was recrystallized from hexane, 4-alkoxy-4-42-(4-alkoxypheny)V)ethyl]bipheny/l/(Ia
] was obtained in a yield of 40-60%. Its structure is IR and 'H
- Confirmed by NMR spectrum.

Compounds CIc1 and [■d] obtained in Examples 3 and 4
The phase transition temperature of is shown in Table 1.

Example 6 [Compound N[133] Yield 40%r R,,K
Br diak (,, -1)"H-NMR: δC,Z
Cj3 (ppm) 2956, 1608. 1512 1254, 824 7.6-6.7 (12H, m).

4.1-3.7 (4H, m).

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^* is an optically active alkyl group having 4 to 13 asymmetric carbon atoms, and R is a carbon A is a straight chain alkyl group with a number of 1 to 20, A is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or a group -O-, X is a hydrogen atom or a fluorine atom, Y
and Z is a group -CH_2CH_2- when Y is a single bond
and when Y is a group -CH_2CH_2-, Z represents a single bond). (2) In the general formula [I], R^* is the general formula [II]
▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] Optically active alkyl represented by (in the formula, l is an integer from 1 to 5, m is an integer from 0 to 5, and * is an asymmetric carbon atom) The optically active liquid crystal compound according to claim 1, which is a group.