JPH0150A - Novel optically active compounds with multiple asymmetric carbon atoms - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organic compound and a liquid crystal composition containing the same, and more particularly to an organic compound containing an optically active group and useful as a component of a ferroelectric liquid crystal composition. The present invention relates to a ferroelectric liquid crystal composition.

(Background of the invention and prior art) Currently, the TN (twisted nematic) type display system is most widely used as a liquid crystal display element.This TN liquid crystal display has many advantages such as low driving voltage and low power consumption. It has advantages.

However, in terms of response speed, they are inferior to light-emitting display elements such as cathode tubes, electroluminescence, and plasma displays. Adjust the twist angle from 180° to 270°
A new TN type display element with a larger value of 0 has been developed, but its response speed is still inferior. Although various efforts for improvement have been made as described above, fully satisfactory performance has not yet been achieved. However, in new display systems using ferroelectric liquid crystals, which have been actively researched recently, there is a possibility of significant improvement in response speed (C1ark et al. Applied P.
hys, 1ett, 36, 899 (1980
)). This method utilizes a chiral smectic phase such as a chiral smectic C phase (hereinafter abbreviated as SC*) that exhibits ferroelectricity. The phase exhibiting ferroelectricity is SC*
Not only the phase, but also chiral smectic F, G%H, I
It is known that these phases exhibit ferroelectricity.

Ferroelectric liquid crystal materials used in ferroelectric liquid crystal display devices that are actually used are required to have many properties, but at present, it is not possible to meet them with a single compound, and there are several It is necessary to use a ferroelectric liquid crystal composition obtained by mixing liquid crystal compounds or non-liquid crystal compounds.

(Object of the Invention) The present inventors have discovered a compound having the property of increasing the spontaneous polarization value Ps -, which is one of the important properties necessary for this ferroelectric liquid crystal composition, and have arrived at the present invention. .

(Structure of the Invention) That is, the present invention relates to the general formula (wherein R1 is a linear or branched alkyl group having 1 to 18 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkoxycarbonyl group, All alkoxycarbonyloxy groups, hydrogen atoms, halogen atoms, or cyano groups are shown, and R2 has 2 to 3 skeletal atoms in the chain.
20 optically active groups, (and (each represents a rogen atom or a cyano group), and t is 1 to 10.
m is an integer of 0 or 1, and * represents an asymmetric carbon atom. ) An optically active compound represented by the following and a chiral liquid crystal group 1 acid compound containing the optically active compound.

To further explain formula (I), R1 is preferably a linear alkyl group or alkoxy group having 4 to 14 carbon atoms. Typical optically active groups for R2 include optically active monohalogenated alkyl groups having 2 to 20 carbon atoms or alkyl groups having an alkoxy branch. can be given. Where,
It may also be an optically active group.

R2 where R3 is a linear alkyl group and X is a halogen atom
Preferred examples include the following.

Preferred examples of R2 in which R3 is an optically active alkyl group and X is a halogen atom include the following.

Next, examples of an alkyl group in which R2 has an alkoxy branch include the following. Here, 83 is the same as above, R
4 is a straight chain or branched alkyl group having 1 to 10 carbon atoms, and R
When 4 is a branched alkyl group, it may be an optically active group. When R3 and R4 are both straight-chain alkyl groups, preferred examples of R2 include ***, and when R4 is an optically active alkyl group, preferred examples of R2 include * * CHs *. It will be done.

When Rs is an optically active alkyl group and 84 is a linear alkyl group, preferred R1 is CHs C
Examples include Hs.

When R3 and R4 are both optically active alkyl groups, preferred examples of R2 include CHI CHs CHs CHI.

In addition, the following percentages are preferable: There are various things that can be mentioned.

It is shown in Table 1.

(Effects and Actions of the Invention) The compound represented by the general formula (1) of the present invention is characterized by a large spontaneous polarization value (Pg) or a large potential spontaneous polarization value.

According to measurements by the present inventors, the PsO value is 94 nC at 25°C when, for example, the compound of Example 1 described below is measured by extrapolation.
/d. Since this value has not been measured for the compound itself, it cannot be said that this value is the Pg of the compound itself, but in practical use, something with such an effect is extremely useful.

On the other hand, the patent application filed by the present inventors on 138.2.1986
Pa? of the compound of the following formula described in No. 69? When measured, 2
It was 57 nC/d at 5°C. Compound (2), in which the linear acyl group of compound (6) was changed to an optically active substituent acyl group, had a Ps value approximately twice that of compound (b). That is, compound (6) is further added with 1 asymmetric carbon.
By introducing these elements, the value of P8 can be significantly increased. As a result, a total of 10 compounds of formula (1) of the present invention
The ferroelectric composition containing 100μ at 25°C
A response time as short as sec can be achieved.

Further, by adding an appropriate amount of the intermediate compound of the present invention to a chiral or non-chiral smectic liquid crystal compound or a chiral smectic liquid crystal composition, the Pg thereof can be significantly increased.

In formula (1), the absolute configuration of each asymmetric carbon may be either the R-configuration or the S-configuration.

The chiral pitch of the chiral nematic liquid crystal composition obtained by adding the compound of the present invention to the nematic liquid crystal composition is very short as illustrated in the examples, and it can be said that it is very useful as a pitch adjusting material for the chiral nematic liquid crystal composition. .

Furthermore, its temperature dependence δPFi is small as exemplified by the example. Currently known pitch control materials for chiral nematic liquid crystal compositions, such as (S)-4-(2'-methylbutyl)-4'-cyanobiphenyl, have a δP of 0 under the same conditions.
．． 543, and compared to this, the δ of the compound of the present invention is
It can be seen that P is small. Twist angle with TN type
In a so-called super TN type display having an il of 80' to 2700, it is desirable that the temperature dependence of the pitch be small, because if the temperature dependence of the pitch is large, the display quality will be significantly degraded. The Super TN type designation contains the compounds of the present invention. When a chiral nematic liquid crystal composition is used, since the temperature dependence of pitch is small, an excellent super TN type display element with little deterioration in display quality can be produced.

[Production method of compound]

The compound of formula (I) is produced, for example, by the route shown in the diagram below (in the above formula, R1, R2, t%ms 4Σ, -=D have the same meanings as above). Here, the condensing agent is N,N-dicyclo Hexylcarbodiimide and the like are preferred.

(Examples) Hereinafter, the compounds and liquid crystal compositions of the present invention will be explained in detail with reference to Examples.

Example 1 ((2'8.2''5)-4'-octyloxy-4-(
2'-(2''-butoxypropionyloxy)propoxy)biphenyl (in formula (1), R1 is an octyloxy group, %1@@-1 t is 1, m is 0, R2 is -CH-0- C4Ho's,
Zhan Xun CH socu.

(1) (■-1-(4'-octyloxy-4-biphenyloxy)-propan-2-ol production literature (C-
Malanga et R48ynthet1e Co
mmunications, 12 (1), 67
-70 (1982) ) K thus produced (28)
-2-tetrahydropyranyloxy-1-hydroxypropane 137v (0.85 mol) and anhydrous pyridine 600
The mixture of f was cooled on ice, and a solution of p-) luenesulfonyl chloride 165F (0.87 mol) in pyridine 200d was added dropwise thereto, and the mixture was stirred at 0°C for 2 hours, then at room temperature for 2 hours, and then stirred at room temperature for 2 hours. I left it overnight.

Add toluene IIl and then add 2N-NaOH solution 5
00d was added and the organic layer was separated and washed several times with water to make it neutral. After drying (using !IJUN SRIA), the solvent was distilled off to give (28) -2-(2'-tetrahydrohyranyloxy)-1-(p-)luenesulfonyloxy)-propane 257f. (yield 95.9%).

Sodium hydride (60%) 2F,4-hydroxy-4
'-Octyloxy biphenyl 10f1 In a mixture of 200-tetrahydrofuran (hereinafter abbreviated as THF),
(28)-2-(2'-tetrahydropyranyloxy)
-1-(p-toluenesulfonyloxy)-propane 2
0f.

300 g/solution of ON, N-dimethylformamide (hereinafter abbreviated as DMF) was added and stirred at 60° C. for 4 hours. After cooling to room temperature, add 300 d of toluene and 300 W of water! ? The organic layer was separated, washed with alkali, water, and concentrated. Tori ethanol 300sd, pyridium P
-) Luenesulfonate (hereinafter abbreviated as PPTS) 2
F was added and stirred at 50°C for 3 hours. Ethanol was distilled off, 300 ml of toluene was added, the organic layer was washed with water, concentrated, and recrystallized to obtain 1-(4'-octyloxy-4) with a melting point of 138.5-140.3°C. -biphenylyloxy)-propan-2-ol 8f was obtained.

(il) (S) Production of -2-butoxypropionic acid (
8-(→-Ethyl lactate 49.4 f (0,4mot)
and 100 f (0.5 moL) of 1-iodobutane, 77.5 f (0.3 mol) of silver oxide was added over 2 hours. 30g of ether after being left at room temperature for 3 days?
' was added to dilute the mixture, and after a while, the ether was distilled off. The residue was washed with a 2N aqueous sodium hydroxide solution and dried over anhydrous magnesium sulfate. This was distilled under reduced pressure (St-2-butoxypropionate ethyl 30.7f (b, p64℃/
7swHg) was obtained.

To this was added 501 t of 5N aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 5 hours. This mixture was poured into 75 liters of 6N hydrochloric acid, and the organic layer was extracted with ether. After washing the organic layer with water, the ether was distilled to give (S)-2-butoxypropionic acid 21.4
I got N.

Also, in the same manner (2)- using methyl lactate as a raw material, (2)-
2-Butoxypropionic acid was obtained.

(2) Production of target compound Add 130 f of N,N-dicyclohexylcarbodiimide (hereinafter abbreviated as DCC) to 500 wt of dichloromethane.
c 0.05rnot) and 4-N,N-dimethylaminopyridine (hereinafter abbreviated as DMAP)2. Of and (1)
(S)-1-(4'-octyloxy-4-
biphenyloxy)-furova/-2-ol and @-2
-Butoxypropionic acid 2.0 ft- was added and stirred at room temperature for 5 hours. After separating the precipitated crystals, 6N-hydrochloric acid, 2N
- Washed with aqueous caustic soda solution. After further washing with water until the washing liquid becomes neutral, dichloromethane gold is distilled off, and the residue is recrystallized from ethanol to obtain the desired (2'8°2"S) -
4'-octyloxy-4-(2'-(2''-butoxypropionyloxy)propoxy)biphenyl (mp5
0.0°C, (a)”D-41-7(C5,CHCts
)) 8.0ft? Obtained.

In the above (using ■-2-butoxypropionic acid instead of 8-2-butoxypropionic acid, C2'S,
f8)-4'-octyloxy-4-(2'-(2"-
Butoxypropionyloxy)propoxy)biphenyl (rnp, 41.0°C) f was obtained.

Example 2 ((2'S, 2"S, 3"S) -4'-octyloxy-4-(2'-(2"-chloro-3"-methylvaleroyloxy)propoxy)biphenyl ((1 ) In the formula, R1 is an octyloxy group, Kshinseki Σ is ()(X%t
is 1, m is 0] (1) Production of (28,3S)-2-chloro-3-methylpentanoic acid L-inleucine 105f was added to 6N-hydrochloric acid 11, stirred, and cooled on ice. 80f'f of sodium nitrite was added thereto and stirred at 0°C for 3 hours. To this was added 300 d of ether to separate the organic layer, the aqueous layer was further extracted with 150 ml of ether, and the organic layers were combined and dried over magnesium sulfate.

The ether was distilled off and the residue was distilled under reduced pressure to give 34.2N
(28,38)-2-chloro-3-methylpentanoic acid (b, p96-97/4 fiHg>) was obtained.

(11) Preparation of target compound To 300 liters of dichloromethane:
．． Of and DCC15, Of and DMAP2, and Of were dissolved. This (23.38)-2-chloro-3-methylpentanoic acid 9. obtained with K(1). Of was added and stirred at room temperature for 6 hours. Precipitated crystal 1 [organic layer after separation? Washed with 6N hydrochloric acid. The organic layer was washed with water until the washing solution became neutral.

The organic layer was distilled off and the residue was recrystallized from ethanol to obtain the desired (2'8.2"S, 3"5)-4'-octyloxy-4-(2'-(2"-chloro- 4.0 g of 3"-methylvaleroyloxy)propoxy)biphenyl was obtained. The melting point of this product was 69.7°C.

Example 3 ((2′8.2”R)-4′-octyloxy-4-(
2'-(2''-propoxyprobionyloxy)propoxy)biphenyl (in formula (1), () (arrow, t is 1
, m is 0, and R2 is CH.

-CH0-CsHy, i.e. *Production] (1) ■ Production of -2-propoxypropionic acid ■ - Methyl lactate 52.1F (0.5 mol) and 1-iodopropane 10 (1 (0.59 mol) silver oxide in a mixture with 87.5
f (0.38 mol) was added over 3 hours. After leaving it at room temperature for 4 days, dilute with 200 g/e of ether and
Afterwards, the ether was distilled off. The residue was washed with a 2N caustic soda washing solution and then dried over anhydrous sodium sulfate. This was distilled under reduced pressure to obtain methyl 46.1f (b, p33-34°C, 75mHg) of -probyloxyprobionic acid. (2)-Methyl propoxypropionate 28.2j
60 s+/ of water and 10 f of sodium hydroxide were added to F, and the mixture was stirred at room temperature for 3 hours. This was poured into 80 Il/6N hydrochloric acid and the organic layer was extracted with ether. After washing the organic layer with water, the ether was distilled off to give ■-proboxyprobionic acid 18. Of
'i got it.

(11) Production of target compound DCC18, □f (0,06
mol), DMAP 2.0f and 6)-1-(4'-octyloxy-4-biphenylyloxy)-propane-2
-All 7, Of'1lII, 9.

To this was added the (he)-propoxypropionic acid 7 obtained in (+), and the mixture was stirred at room temperature for 4 hours. After separating the precipitated crystals tp, they were washed with 6N hydrochloric acid and 2N aqueous sodium hydroxide solution. After washing with water until the washing solution becomes neutral, dichloromethane is distilled off, and the residue is recrystallized from ethanol to obtain the target compound, i.e., (2'S, 2"R) -4'-octyloxy-4-( 1.5 ft of 2'-(τ-propoxypropionyloxy)propoxy)biphenyl was obtained.The melting point of this product was 52.0°C.

Example 4 [(2"8.2"R)-5-nonyl-2-(4'-(z
/-(2#-propoxypropionyloxy)7'o
poxy)phenyl)pyridine (CH in formula (I).

t is 1, m is 0. R" is -CH-0-CsHy,
* Production of (S)-5-nonyl-2-(4'-(τ-hydroxypropoxy)phenyl)pyridine (11 points 77.6-80
．． 3°C) and (6)-2-propyloxypropionic acid prepared in Example 3. 2"S,2"R)-5-nonyl-2-(4'-(2#-
(2'-propoxyprobionyloxy)propoxy)
phenyl)pyridine was obtained. The melting point was 53.0°C.

Example 5 ((2'R12I'R)-4'-octyloxy-4-
(2'-methyl-3'-(2''-ptoxypropionyloxy)propoxy)biphenyl (in formula (1), R
1 is an octyloxy group, (now Σ is 4) (prevention, t is 11m is 1, Hs R2 is -CROC,H, i.e. production of *) (6) -2-Methyl-3-hydroxypropion Methyl acid 25f, 3,4-dihydrobilane 21g, concentrated sulfuric acid 2
50 g of ml% anhydrous dichloromethane was mixed with water cooling and left overnight. Washed with 5% sodium bicarbonate solution, dried over magnesium sulfate, evaporated the solvent, and distilled the residue under reduced pressure to give 15 g of bp'12-96°C
)-2-Methyl-3-(2-tetrahydropyranyloxy)propionate 4ON was obtained.

Lithium aluminum hydride 7f? Suspend in 50 d of THF and add the total amount of methyl T-2-2-methyl-3-(2-tetrahydropyranyloxy)propionate under cooling.
A HF200 resistant solution was added dropwise. After the reaction, water and a 2N aqueous sodium hydroxide solution were added, inorganic substances were separated, dried over magnesium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure. S)
36 f% of -2-methyl-3-(2-tetrahydropyranyloxy)-furopan-1-ol was obtained.

15fg of this product was dissolved in 500ml of pyridine, and two drops of p-toluenesulfonyl chloride (16.4f'D 7,100nt) dissolved in 7100nt of pyridine were added under cooling with water. After extracting toluene 3nO*, it was washed with water, dried over sulfuric acid, and the solvent was distilled off to give 259 was obtained.

Suspend 2.0 y of sodium hydride (55%) in THF, add 200 g 1 liter of THF solution of 101 iF of 4'-octyloxy-4-hydroxy-biphenyl under water cooling, and add the above (FO-1-(P-) luenesulfonyloxy)-2-methyl-3-(2-tetrahydropyranyloxy) propane 15 jl dimethylformamide 3
00 ml of the solution was added and stirred at 60° C. for 5 hours. After cooling, 500 ml of toluene was added, washed with water and an alkali, and the solvent was distilled off. To this was added 300 ml of ethanol and 3 ft of p-toluenesulfonic acid monohydrate, and the mixture was heated at t50°C for 1 hour. After cooling, a crystal is grown under cooling, and this tF
Then, @-4'-octyloxy-4-(2-methyl-3-hydroxy-propoxy)biphenyl t i yt with rmp 128°C was obtained. This product 1f, (th)-2-butoxypropionic acid obtained in Example 1, 0.61, DC
C1,01, DMAPo, 1F and dichloromethane 30
ml of the mixture t'' was stirred at room temperature for 6 hours, the solid produced was separated in a furnace, the mother liquor was washed with acid, alkali and water, then dried over magnesium sulfate, and the solvent was distilled off.

The residue was purified by column chromatography packed with activated alumina, and then recrystallized from ethanol.
2'R,2''R) -4'-octyloxy-4-(2
'-Methyl-3'-(2!'-ptoxyglobionyloxy)propoxy)biphenyl 0.6F! Obtained. The melting point of this product was 42.6°C.

The results of Examples 1 to 5 above and the melting points of other compounds of the present invention are shown in Table 1.

Example 6 (Use Example 1) A composition having an SC phase consisting of six types of achiral compounds having the following composition was prepared.

The phase transition temperature of this composition was as follows.

When 1 Oi amount % of the compound of Example 1 (Sample No. 6), which is one of the compounds of formula (1) of the present invention, was added to this composition, it showed ferroelectric properties in the temperature range of 16°C to 50°C. An SC* phase was observed. The spontaneous polarization of this composition at 25° CK was 9.4 nC/d1 and the Telt angle was 16.7°. This composition was used as an alignment treatment agent: cPVA was applied, and the surface was injected into a cell with a thickness of 2 μm equipped with transparent electrodes subjected to parallel alignment treatment, and the cell was further exposed to two sheets of polarized light at right angles to each other. When a square wave of ±10V was applied to the device, changes in transmitted light intensity were observed. The response time was determined from the change in transmitted light intensity at this time and was 100 μsec at 25°C.

As described above, it can be seen that by using the compound of the present invention, spontaneous polarization can be imparted to a non-chiral smectic composition, and a ferroelectric liquid crystal composition having a high-speed response at room temperature can be obtained.

Example 7 The chiral pitch of a chiral nematic liquid crystal composition obtained by adding 1 ft 131% by weight of the compound of Example 1 (sample 1'h6) to ZLI-1132 manufactured by Merck & Co., Ltd. at 25°C by the total cartridge method. The thickness was 15 μm. Furthermore, the temperature dependence δP of the pitch shown in the formula is t-20°C1t
, 0.478 at -60°C.

that's all

Claims (7)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (However, in the above formula, R^1 is a straight or branched alkyl group having 1 to 18 carbon atoms, an alkoxy group, an alkanoyl group,
It represents an alkanoyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, a hydrogen atom, a halogen atom, or a cyano group, and R^2 indicates that the number of skeletal atoms in the chain is 2.
~20 optically active groups are shown, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are each independently ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (X represents a hydrogen atom, a halogen atom, or a cyano group) . Further, l is an integer of 1 to 10, m is 0 or 1, and * represents an asymmetric carbon atom. ) An optically active compound represented by (2) An optically active compound according to claim (1), wherein R^2 in formula (I) is an optically active monohalogenated alkyl group having 2 to 20 carbon atoms. (3) An optically active compound according to claim (1), wherein R^2 in formula (I) is an alkyl group having an alkoxy branch. (4) A chiral liquid crystal composition containing at least one optically active compound represented by formula (I) according to claim (1). (5) Claim (4) exhibiting a chiral smectic liquid crystal phase
) chiral liquid crystal composition described. (6) Claim (4) exhibiting a chiral nematic liquid crystal phase
The chiral liquid crystal composition described above. (7) A liquid crystal display element constructed using the liquid crystal composition according to claim (4).