JPS59190959A - Ester derivative of 2-cyano-4-substituted phenol - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formulas I ' and II' (R is 1-15C alkyl; X is F, Cl or 1-15C alkyl). EXAMPLE:2 -Cyano- 4 -chlorophenyl-trans-4''-propyl-trans-octadecahydro-p-terphenyl-trans-4 -carboxylate. USE:A liquid crystal composition, capable of exhibiting the liquid crystal phase within a wide temperature range, and having negative dielectric anisotropy. PREPARATION:A compound expressed by formula II is hydrolyzed in a diethylene glycol system to give a compound expressed by formula III, which is reacted with thionyl chloride and converted into an acid chloride expressed by formula IV'. The resultant compound expressed by formula IV' is then reacted with a 2-cyano-4-substituted phenol to afford a compound expressed by formula I '. On the other hand, the compound expressed by formula III is reduced with metallic sodium and reacted with thionyl chloride to give an acid chloride expressed by formula V, which is then reacted with a 2-cyano-4-substituted phenol to give the aimed compound expressed by formula I ''.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal compound that exhibits a liquid crystal phase over a wide temperature range and has negative antistatic anisotropy, and a liquid crystal composition containing the same.

Depending on the style, TN type (twisted nematic type), DS type (
There are various types such as dynamic scattering type, guest-host type, and DAP type, and the properties of the liquid crystal materials suitable for each type are different. All liquid crystal materials are required to be stable against moisture, air, heat, light, etc., and to exhibit a liquid crystal phase over as wide a temperature range as possible, centering on room temperature. At present, there is no single compound that satisfies these conditions, and liquid crystal compositions obtained by mixing several types of liquid crystal compounds and non-liquid crystal compounds are in practical use.

Recently, with the spread and development of liquid crystal usage technology, guest-host type liquid crystal display devices, which are one type of color liquid crystal display method, have been attracting attention. This uses a mixture of liquid crystal and dye.A liquid crystal having negative dielectric anisotropy is used in a positive guest-host type display element.

Therefore, there is a need for liquid crystal compounds having various properties, good compatibility, and negative dielectric anisotropy that can be used as constituent components of liquid crystals.

An object of the present invention is to provide a novel liquid crystal compound suitable for such uses.

That is, the present invention is based on the general formula (in the above formula, () is () or XX, R is an alkyl group having 1 to 15 carbon atoms, and X is F or Ct or an alkyl group having 1 to 15 carbon atoms) The present invention relates to an ester derivative of 2-cyano-4-substituted phenol represented by the following formula (indicating that 2-cyano-4-substituted phenol) and a liquid crystal composition containing at least one thereof.

The compounds of the invention have a high clearing point, for example trans-47-propyl-trans-octadecahydro-p-terphenyl-trans-4, which is one of the compounds of the invention.
- Crystal of carvone v-2-cyano-4-1' lorophenyl ester - Nematic point is 160.5°C, 4matic - Clearing point is 267.0°C, which shows a liquid crystal phase in a wide temperature range. By adding it as a component of the composition, the clearing point can be raised without increasing the viscosity of the liquid crystal composition. Further, the dielectric anisotropy value of the compound of the present invention is -3
By mixing with other nematic liquid crystals, it is possible to obtain liquid crystal compositions with negative dielectric anisotropy that can be used for guest-host type display devices, and the dielectric anisotropy value By combining it with a positive one, it can be used in a dual frequency method display element.

Next, a method for producing the compound of the present invention will be shown.

Compound (1') where (y is (y) in general formula (I)
A method of manufacturing is shown. 4-() Lance-4-() Lance-4 by the method disclosed in JP-A-58-10552
-Furkylcyclohexyl)cyclohexyl)benzonitrile (compound (1)) was prepared and hydrolyzed in-system with an aqueous potassium hydroxide solution and diethylene glycol to produce 4-(trans-4-(trans-4-alkylcyclohexyl)cyclohexyl) Benzoic acid (compound (a)
) is manufactured. Next, thionyl chloride was reacted to obtain acid chloride (compound side), and then 2-cyano-
4-[trans-4-(
) lance-4-alkylcyclohexyl)cyclohexyl]benzoic acid-2-cyano-4-substituted phenyl ester (compound (1'l) is obtained.

Next, a method for producing a compound (1) in which the sha is XX in the general formula (1) will be shown.The benzoic acid-derived compound (1) prepared during the production of the above-mentioned compound (1') is mixed with in-amyl alcohol. trans-4"-alkyl-trans-
Octadecahydronyl-terphenyl-trans-4-
A carboxylic acid (compound GV15) is obtained. It is then reacted with thionyl chloride to give the acid chloride (compound (V)) and then reacted with 2-cyano-4-substituted phenol in pyridine to give trans-47-alkyl-trans-octadecahydro-p-terphenyl. 2-cyano-4-substituted phenyl of -trans-4-carboxylic acid (compound (I')) is obtained.

The above is expressed as a chemical formula as follows.

6-0 (Y') (In the above formula, R and X are the same as above.) The compounds of the present invention will be explained in more detail below with reference to Examples.

In each example, the crystalline phase is abbreviated as C, the nematic phase as N5, and the transparent phase as ■.

Example 1 4-()trans-4-(trans-4-propylcyclohexyl)cyclohexyl) benzoic e-2
-Production of cyano-4-fluorophenyl ester (compound (I') in which R caf'lovyl group, ■ is 0, and X is F) (1) 4-()trans-4-(trans-4-propylcyclohexyl) Production of cyclohexyl]benzoic acid (compound (III)) 5 g of 4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzonitrile produced by the method disclosed in JP-A-58-10552 was hydroxylated. A solution of 5y of potassium dissolved in 10t of water was added to 100y of diethylene glycol and heated in a flask at 200°C for 7 hours.After the reaction was completed, it was cooled to room temperature, and 50l of 6N-hydrochloric acid and 100g of water were added. .The precipitated crystals were filtered, thoroughly washed with water and thoroughly dried.
-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzoic acid (compound ([)) 5
I got g.

(2) Esterification of 4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzoic acid (compound ([))
0.911 and 10 tnl of thionyl chloride were placed in a total flask and heated at 80°C for 1 hour to obtain a homogeneous system. Then, excess thionyl chloride was distilled off under reduced pressure, and the oily acid chloride residue 5-fluorosalicylaldehyde oxime 45f was dissolved in 100 g of acetic anhydride and refluxed for 10 hours. After the reaction, acetic anhydride was distilled off under reduced pressure L7, and to the remaining oil, a solution of 22f potassium hydroxide dissolved in 100ml of water and 1ml of ethanol were added, and the mixture was heated at 80°C for 5 hours. After being brought to room temperature, 6N = Completely acidified with hydrochloric acid to precipitate crystals 9- The crystals were filtered, dried and recrystallized with methanol, and the melting point was 120-122°C and the yield was 80 f. Met.

After the mixture was left to stand, 20 ηtW of toluene was added and then poured into water. The toluene layer was separated, washed with 6N hydrochloric acid, 2N sodium hydroxide solution, and water, and then dried by mixing with anhydrous sodium sulfate. Next, toluene was distilled off under reduced pressure and the obtained solid was recrystallized with ethyl acetate to obtain the desired product.
4-(trans-4-()trans-4-propylcyclohexyl)cyclohexyl) 2-cyano-benzoate
0.88f (yield 66.9%) of 4-fluorophenyl ester (compound (1')) was obtained.

The C-N point of the compound (I') is 112.9°C, N-I
The point was 20B, 7°C.

Example 2 4-() Lance-4-(Trans-)〇
- 4-propylcyclohexyl)cyclohexyl) 2-cyano-4-chlorophenylnisder benzoate (1(
Compound (1') in which a propyl group, ■ is ◎, and X is Ct
) Production (1) Production of 2-cyano-4-chlorophenol 20f of 5-chlorosalicylaldehyde oxime was dissolved in 100 ml of acetic anhydride and refluxed for 10 hours. After the reaction, acetic anhydride was distilled off under reduced pressure. A solution of 2017 potassium hydroxide dissolved in 10011 Il of water and 100 g of ethanol were added to the remaining oil, and the mixture was heated at 80°C for 5 hours. The mixture was then brought to room temperature and completely acidified with 6N hydrochloric acid to precipitate crystals, which were filtered and dried. The yield of the dried product was 14f5 with a melting point of 164-168°C.

(2) 4-(trans-4-()trans-4-propylcyclohexyl)cyclohexyl]
From benzoic acid (compound (1)) 1.061 and the above 2-cyano-4-chlorophenol 0.541, 4-[trans-4-(trans-4-'lovylcyclohexyl)
Cyclohex "A') Benzoic e-2-cyano 4-chlorophenyl ester (compound (1')) 0.881
(yield 58.9%). The C-N point of this compound is 180.1°C, and the N-I point is 247.0'
It was C.

Real mN8 trans-4"-propyl-trans-ocpdecahydro-p-terphenyl-trans-4-carboxylic acid-2-cyano-4-fluorophenyl ester (R cafu'lovir group, ■ is 0, X is F Production of compound (I")) 4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzoic acid (compound @)) a
Stirred with gt=1500 ml of isoamyl alcohol and heated to 90°C.

Next, 10 y of metallic sodium was added and a vigorous reaction was continued.After 3 hours, 8 y of metallic sodium was further added to the reflux.
0 g was added to obtain a homogeneous reaction solution.

After addition, the precipitate was completely acidified, filtered, thoroughly washed with water, and then recrystallized with acetic acid to obtain trans-4"-propyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid ( Compound d) was obtained.The yield of small compound was 1.9f1 yield was 68%, it exhibited liquid crystallinity, and its C-8 point was about 170°C, and its S-N point was 282°C.
, N-I point was 290-300°C (with decomposition).

1.48 y of the carboxylic acid (compound (Ivf)) was heated to 80°C with 10 vtl of thionyl chloride.
The reaction was continued for an additional 1.5 hours until the mixture became uniform. Excess thionyl chloride was distilled off under reduced pressure to obtain an oily residue of acid chloride (compound α). 0.60 f of 2-cyano-4-fluorophenol was dissolved in 5 ml of pyridine and stirred well to react with the acid chloride (compound (V)).

13- After the reaction, leave it overnight and add 20 trtl of toluene.
Pour into water, then separate the toluene layer, add 6N-hydrochloric acid,
After washing with water and an IJium solution (N-hydroxide), it was dried using anhydrous sodium sulfate. Toluene was distilled off under reduced pressure, and the remaining solid was dissolved in ethyl acetate and recrystallized to obtain the target product, trans-4''-propyl-trans-offtate hydrop-terphenyl-trans-4.
-Carboxylic acid-2-cyano-4-fluorophenyl ester (compound (I”)) was converted to 1.20f (yield 63.8%).
)Obtained. The C-N point of the compound (■”) is 190.4°C
%N-I point is 24.6. It was OoC.

Example 4) Lance-4"-propyl-trans-octadecahydro-f-terphenyl-trans-4-carboxylic acid-2-cyano-4-10 lophenyl ester (
R is a propyl group, ■ is 0. Preparation of compound (1) in which X is Ct A method according to Example 8 was followed except that 2-cyano-4-chlorophenol was used in place of 2-cyano-4-fluorophenol. The target compound was obtained. The C-N point of the compound is 160.5°C3N-I point is 2
It showed 67.0°C.

Example 5 4-()trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzoic acid-2-
Production of cyano-4-hebutylphenyl ester (compound (I') where R is a propyl group, ◎ is ◎, and X is a heptyl group) 4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl) benzoin acid (compound ([)
)0.61g and thionyl chloride 10w1 in a flask at 80%
After 1 hour of reaction at °C, a uniform thread was obtained. Excess thionyl chloride was then distilled off under reduced pressure to obtain an oily residue of acid chloride (compound (r)).

Separately 2-cyano-4-hebutylphenol 0, 4.2
f was dissolved in 5 ml of pyridine, and the above-mentioned acid chloride (compound (IV')) was added while stirring well. After the reaction, the mixture was left to stand overnight, then 20 tttt of toluene was added, and the mixture was poured into water.

The toluene layer was then separated, washed with 6N hydrochloric acid, 2N sodium hydroxide solution, then water, and then dried over anhydrous sodium sulfate. Next, toluene was distilled off under reduced pressure, and the remaining solid was dissolved in ethyl acetate and recrystallized to obtain the target product, 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)benzoic acid-2-
Cyano-4-hebutylphenyl ester was added to 0.65y (
Yield: 66.4%).

The C-N point of the ester is 73.6°C, and the N-I point is 221.
．． It was 7°C.

Example 6 trans-4”-propyl-trans-octadecahydro-p-terphenyl-trans-4-carbon e-2-cyano-4-hebutylphenyl ester (
Preparation of compound (I") in which R caf'ropyl group, ■ is O, and X is heptyl group. [)) 1.27F was heated to 80°C with 10 stt of thionyl chloride. After 2 hours, the reaction solution became homogeneous,
The reaction was continued for an additional 1.5 hours. Next, excess thionyl chloride was distilled off under reduced pressure to obtain an oily residue (compound (■")) which is an acid chloride. Separately, 0.86 f of 2-cyano-4-hebutylphenol was dissolved in 5 ml of pyridine. Set aside, add the acid chloride (compound (ff)) while stirring well.
)) and Δ. After reaction - Leave to stand overnight, then add toluene 20
Add +/, pour into water, separate toluene layer, 6N-hydrochloric acid, 2N-sodium hydroxide.

The solution was then washed with water and dried using anhydrous sulfuric acid. Next, toluene was distilled off under reduced pressure, and the remaining solid was dissolved in ethyl acetate and recrystallized to obtain the target product, trans-4"-propyl-trans-octadecahydro-p-terphenyl-trans-4. -Carboxylic acid-
2-cyano-4-heptyl phenyl ester 1.31
f (yield 647%) was obtained. The C-N point of this compound is 84.
6°C, and the N-I point was 247.6°C.

Example 7 (Usage example) 17- Regarding the characteristics of the ester-based nematic liquid crystal composition (Chisso (Rixon FN-45 manufactured by Kiki)), the N-I point is 68
．． 4°C, △t is -0, 9, 20°C viscosity is 1
It is 8.5 cp. A guest-host cell was prepared by adding 1% by weight of a commercially available dye (G-224, manufactured by Merck & Co., West Germany) to the composition, and the threshold voltage was measured to be 8.80 V. . Next, the compound of the present invention, 4-()trans-4-(trans-4-propylcyclohexyl)cyclohexyl)benzoic m-2
-cyano-4-chloro7enyl ester (according to Example 2) 10 parts by weight, trans-4"-propyl-trans-octadecahydro-p-terphenyl-trans-4
- Bore e-2-cyano 4-chlorophenyl ester (according to Example 4) 5! Part i and above FN-45
A liquid crystal composition containing 85 parts by weight was prepared. That N-I
The point is 82.3°c5Δε=1.2.The viscosity at 20°C is 80. Ocp and further the above-mentioned dye G-2
When a guest/host cell was prepared with 1% by weight of 24 added thereto), the threshold voltage was measured and was significantly lowered to 8.20V.

Example 8 (Usage Example) Regarding the initial characteristics of an ester-based nematic liquid crystal composition (Rixon FN-45 manufactured by Chisso ■), the N-I point was 68,
4°C1Δε has a viscosity of 1B at -0, 9, and 20°C
, 5 cp. A guest-host cell was prepared by adding 1% by weight of a commercially available dye (G-224, manufactured by Merck & Co., West Germany) to the composition and encapsulating it in a cell with a distance between opposing electrodes of 10 μm, and its threshold voltage was measured. The voltage was 8.80V. Then, 10 parts by weight of the compound of the present invention, 4-(trans-4-()trans-4-propylcyclohexyl)cyclohexylamine, [[-2-cyano-4-heptylphenyl ester (according to Example 5)], trans −
4"-propyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-2-Schiff/-
4-Hebutylphenyl ester (according to Example M 6) 10
A total liquid crystal composition was prepared consisting of parts by weight and 80 parts by weight of the above-mentioned FN-4. The N-I point is 95.2°C5△ε
showed a viscosity of 82.8 cp at -1, 2, and 20°C, and a guest-host cell was made with 1% by weight of the aforementioned dye G-224, and its threshold voltage was measured and found to be 3.26V. It decreased significantly.

that's all

Claims (2)

[Claims] (1) General formula (In the formula, () is (y and L< is -0-, R is an alkyl group having 1 to 15 carbon atoms, and X is F or Ct
or an alkyl group having 1 to 15 carbon atoms). (2) General formula (in the above formula, the symbol is 0 or XX, R is an alkyl group having 1 to 15 carbon atoms, and X is F or Ct or an alkyl group having 1 to 15 carbon atoms) A liquid crystal composition containing at least one 2-cyano-4-substituted phenol ester derivative represented by the following formula.