JPH0672125B2 - Trans-ethylene derivative compound and liquid crystal composition containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a trans-ethylene derivative compound used in a liquid crystal electro-optical element and a liquid crystal composition containing the same.

[Prior Art] Liquid crystal surface elements have begun to be used in various applications such as watches, calculators, measuring instruments, automobile instruments, copying machines, and cameras in recent years, and have a wide operating temperature range and low operating voltage. Various performance requirements such as high-speed response, chemical stability, etc. are made. However, at present, there is no material satisfying all of these characteristics with a single material, and a plurality of liquid crystal and non-liquid crystal materials are mixed to satisfy the required performance as a liquid crystal composition. Therefore, it is desired to develop a liquid crystal or non-liquid crystal material that is excellent in one or two or more characteristics, not all of the various characteristics.

[Problems to be Solved by the Invention]

Among various characteristics required for liquid crystal compounds used in the field of display devices, it is important to provide a material exhibiting a nematic phase in a wide temperature range including room temperature and having excellent compatibility with other liquid crystals or non-liquid crystals. It is a problem.

[Means for solving problems]

The present invention provides a novel material to solve the above-mentioned problems. (In the formula, -CH = CH- represents a trans-1,2-disubstituted ethylene bond, and Z is [R represents a linear alkyl group having 1 to 8 carbon atoms, Represents a trans-1,4-substituted cyclohexane ring].

The general name for the compounds of general formula (I) is 4- (trans-n-pente-3'-nyl) phenyl ester.

Compounds of general formula (I) of the present invention has a practical temperature range in the transition temperature to an isotropic liquid phase from the nematic phase (T _C), a stable material in the chemical, the liquid crystal composition Even if mixed with other compounds necessary to form
It is a material with extremely excellent compatibility without increasing the viscosity.

The compound of formula (I) of the present invention is used as a liquid crystal composition by mixing at least one kind with other liquid crystal and non-liquid crystal.

Examples of substances to be mixed as the compound of the present invention are as follows. In the following formula, R is different from R in the present invention, and R and R'represent an alkyl group, an alkoxy group, a halogen atom, a cyano group or the like.

Note that these compounds are merely examples, substitution of a hydrogen atom with a halogen atom, a cyano group, a methyl group, etc., substitution of a cyclohexane ring, a benzene ring with another 6-membered ring, a 5-membered ring, etc. Various materials are selected and used, such as changing the bonding group between them.

The compound of the present invention is disposed as a liquid crystal composition between substrates with electrodes and can be used in various modes such as twist / nematic mode, dynamic scanning mode, guest-host mode, and phase-changing mode.

This liquid crystal surface element is one in which the compound of the present invention is disposed as a liquid crystal composition between substrates with electrodes, and specifically, on a substrate such as plastic or glass, if necessary, iO ₂ , Al
_After undercoating ₂ O ₃ etc. and providing electrodes such as In ₂ O ₃ --SnO ₂ etc. and patterning, if necessary, polyimide, SiO ₂
Etc. to form an overcoat, orienting the same, printing a sealing material on it, arranging the electrodes so that the electrode surfaces face each other to seal the periphery, and curing the sealing material; Is injected and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, a polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflection plate, a reflection plate, a light guide plate, an ultraviolet cut filter, etc. are laminated on this liquid crystal cell, characters and figures are printed, and non-glare processing is performed. A liquid crystal element is obtained by performing the above steps.

Note that the above description merely shows the basic configuration and manufacturing method of the liquid crystal element, and for example, a substrate using a two-layer electrode,
Various structures such as a two-layer liquid crystal cell in which two liquid crystal layers are formed can be used.

The compound of the general formula (I) of the present invention is produced, for example, according to the following method.

That is, first, p-bromophenol (II) is reacted with benzyl chloride in the presence of potassium carbonate in an acetone solvent to give p-bromobenzyloxybenzene (III). Next, trans-n-pente-3-nyl-1-promide (RM Coates et al., J. Org. Chem., 47 , 3597 (198
2)) (IV), a Grignard reagent prepared from magnesium, and (III) are reacted in the presence of a coupling catalyst such as Ni (dppe) Cl ₂ to give 4- (trans-n-
Pente-3'-nyl) -benzyloxybenzene (V)
To get This (V) is reacted with metallic sodium in n-butanol to give 4- (trans-n-pente-3'-
Nil) -phenol (VI), which is reacted with thionyl chloride of the compound of formula (VII) in the presence of pyridine to give the acid chloride (VIII). The compound of

Note that this manufacturing method is merely an example, and various manufacturing methods can be used.

〔Example〕

Hereinafter, the method for producing the compound of the present invention and the liquid crystal composition using the compound of the present invention will be described in more detail with reference to Examples.

Example 1 First Stage To 135 g (0.782 mol) of p-bromophenol (II), 104 g (0.822 mol) of benzyl chloride and 162 g (1.1 g of potassium carbonate).
74 mol) and acetone 1.0 were added, and the mixture was refluxed for 14 hours. After removing the salt and distilling off the solvent, 650 ml of toluene was added and 2
% Sodium hydroxide and water were washed in this order, concentrated and recrystallized with ethanol to obtain 144 g of p-bromobenzyloxybenzene (III). Yield 70%.

Second stage To 144 g (0.547 mol) of p-bromobenzyloxybenzene (III) obtained in the first stage, 158 g (1.06 mol) of trans-n-pent-3-yl-1-promide (IV) and magnesium 30.4 g (1.27 mol), tetrahydrofuran 8
The Grignard reagent prepared from 80 ml was added dropwise over 1 hour at room temperature in the presence of 352 ml of tetrahydrofuran and 19.5 g (0.037 mol) of bis (1,2-diphenylphosphino) ethane nickel (II) chloride. After stirring at room temperature for 4 hours, 400 ml of 1: 5 hydrochloric acid was added to separate the organic layer, and the aqueous layer was extracted with toluene. The organic layers were combined and washed with water, the solvent was distilled off, and the residue was recrystallized from ethanol to obtain 4- (trans-n-pente-3′-nyl) -benzyloxybenzene (V) (98.2 g). It was Yield 71.2
%.

Third stage 4- (trans-n-pentene-obtained in the second stage
3'-nyl) benzyloxybenzene (V) 31.2 g (0.1
To 24 mol), 900 ml of n-butanol was added, and 120 g of sodium metal was gradually added thereto over 4 hours. afterwards,
After refluxing for 3 hours, 750 ml of 1.3% sodium hydrosulfite was added, and this was added to a solution of 360 ml of acetic acid and 2.8 of water. The upper layer was washed with a saline solution, the solvent was distilled off, and then 4- (trans-n-pente-3 ′) was obtained by distillation.
14.1 g of -nyl) phenol (VI) was obtained. Boiling point 116 ℃ / 2mm
Hg. Yield 70.3%.

Fourth stage trans-4-n-butylcyclohexanecarboxylic acid (in the formula (VII) 1.70 g (9.25 mils), 1.70 g (1
3.9 mmol) and perchlorethylene (8 ml) were added and the mixture was refluxed for 3 hours and then the solvent was distilled off to give 4- (trans-n-pente-3'-nyl) -phenol (obtained in the third step). VI) 1.50 g (9.25 mmol) and pyridine 0.88 g
(11.1 mmol) and 20 ml of toluene were added, and the mixture was further refluxed for 3 hours. Excessively remove the precipitated pyridine hydrochloride,
The solution was washed with dilute hydrochloric acid, water, 2% sodium hydroxide and water in this order, concentrated, subjected to alumina-toluene column chromatography, evaporated to remove the solvent, and recrystallized with methanol to obtain the desired trans-4-n. -Butylcyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester (in formula (I) 2.49g was obtained. Yield 82%, melting point ( _Tm ) 31.8-3
2.0 ° C, clearing point (T _c ) 62.1 ° C, Assignment of ¹ H-NMR (CCl ₄ solvent, TMS internal standard) spectrum was as follows.

δ (ppm) 0.6 to 2.77 (complex m, aliphatic, 26H) 5.10 to 5.39 (m, -CH = CH-, 2H) 6.59 to 7.02 (complex m, aromatic, 4H) IR spectrum of this compound (KBr tablets ) Is shown in FIG. Similarly, the following compounds were synthesized.

Trans-4-methyl-cyclohexanecarboxylic acid 4 '
-(Trans-n-pente-3 ″ -nyl) -phenyl ester trans-4-ethyl-cyclohexanecarboxylic acid 4 ′
-(Trans-n-pente-3 ″ -nyl) phenyl ester trans-4-n-propyl-cyclohexanecarboxylic acid 4 ′-(trans-n-pente-3 ″ -nyl) -phenyl ester melting point (T _m ) 34.4-35.0 ° C, clearing point ( _Tc ) 67.1 ° C trans-4-n-penter-cyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester melting point ( _Tm ) 41.2. ~ 42.0 ° C, clearing point ( _Tc ) 72.3 ° C trans-4-n-hexyl-cyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester trans-4-n-heptyl- Cyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester trans-4-n-octyl-cyclohexanecarboxylic acid 4'-(trans-n -Pente-3 "-nyl) -phenyl ester Example 2 trans-4-n-propylcyclohexanecarboxylic acid 4 '-(trans-n-pente-3" in Example 1
-Nyl) -phenyl ester, trans-4-n-butylcyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester, trans-4
The clearing point (Tc) of an equal weight mixture of -n-pentylcyclohexanecarboxylic acid 4 '-(trans-n-pente-3 "-nyl) -phenyl ester was 66.8 ° C. , 4-ethyl-4'-
57.3 ℃ for mixed liquid crystal containing 15.0wt% of cyanobiphenyl
The clearing point (Tc) was shown.

〔The invention's effect〕

 As described above, the present invention is a novel compound.

General formula (In the formula, -CH = CH- represents a trans-1,2-disubstituted ethylene bond, and Z represents (R represents a linear alkyl group having 1 to 8 carbon atoms, Represents a trans-1,4-substituted cyclohexane ring)) and thereby exhibits a nematic phase in a wide temperature range including room temperature, thereby providing a chemically stable liquid crystal composition. It is an excellent one that produces an effect that can be configured.

[Brief description of drawings]

 FIG. 1 is an IR spectrum diagram of the example of the present invention.

Claims (2)

[Claims] 1. A general formula (In the formula, -CH = CH- represents a trans-1,2-disubstituted ethylene bond, and Z represents [R represents a linear alkyl group having 1 to 8 carbon atoms, Represents a trans-1,4-substituted cyclohexane ring]. ) A trans-ethylene derivative compound represented by 2. General formula (In the formula, -CH = CH- represents a trans-1,2-disubstituted ethylene bond, and Z is [R represents a linear alkyl group having 1 to 8 carbon atoms, Represents a trans-1,4-substituted cyclohexane ring]. ) A liquid crystal composition containing at least one trans-ethylene derivative compound represented by the formula (1) in the composition.