JPH06122648A - Liquid crystal compound and composition - Google Patents

Abstract

PURPOSE:To provide a new liquid crystal compound capable of affording a liquid crystal composition having the relatively high upper limit temperature for chiral smectic C phase by using it as a component of a liquid crystal composition giving the chiral smectic C phase. CONSTITUTION:The objective compound of formula 1 (R<1> and R<2> are each 1-18C alkyl; A<1> and A<2> are each 1,4-phenylene which may be substituted by one to two F atoms). The compound of the formula 1 (where, A<1> and A<2> are each 1,4-phenylene) can be obtained by reaction of a halogenobenzene of formula 2 with an acid chloride of formula 3 in the presence of a Lewis acid (e.g. aluminum chloride) to produce a compound of formula 4, which is then made to react with a compound of formula 5 in an inert gas atmosphere using a palladium catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystal compound useful as a component of a liquid crystal composition used for a liquid crystal display device and the like and a liquid crystal composition containing this liquid crystal compound.

[0002]

2. Description of the Related Art Recently, a display system using a ferroelectric liquid crystal compound has been reported by Meyer et al., And a high speed response and a memory effect of 100 to 1000 times that of a TN type can be obtained. Expectations are high, and research and development are currently underway. The liquid crystal phase of the ferroelectric liquid crystal compound belongs to the tilt-type chiral smectic phase, but in practice, the chiral smectic C phase (hereinafter abbreviated as Sc * phase), which has the lowest viscosity, is practically used. Most desirable. A large number of liquid crystal compounds exhibiting the Sc * phase have already been synthesized and studied, but the conditions for use as a ferroelectric display element are: (a) showing the Sc * phase in a wide temperature range including room temperature, (B) uniform orientation and large spiral pitch, (c) proper tilt angle, (d) low viscosity,
Etc. However, no liquid crystal compound exhibiting the Sc * phase that satisfies these conditions alone has been known, and efforts have been made to satisfy these conditions by mixing. In addition, the development of new liquid crystal compounds exhibiting the Sc * phase is also in progress. On the other hand, as a method for preparing a liquid crystal composition exhibiting a Sc * phase (hereinafter, referred to as Sc * liquid crystal composition), a chiral compound is added to a liquid crystal compound or a composition exhibiting a non-chiral Sc phase without showing ferroelectricity. There is also a method of doing so, and the development of liquid crystal compounds exhibiting the Sc phase is also underway. A racemic liquid crystal compound exhibiting the Sc * phase can also be used as the liquid crystal compound exhibiting the Sc phase. Conventionally, 4'-decyloxy-4- (4-methylhexyloxycarbonyl) tran (described in JP-A-1-221351) related to the applicant's application is known as a tolan-based liquid crystal compound exhibiting the Sc * phase. ing.

[0003]

However, the above compound is
The maximum temperature of the Sc * phase is 51.8 ° C., and development of a compound having a higher Sc * phase or the maximum temperature of the Sc phase is desired as a component of the Sc * liquid crystal composition.

[0004]

The present inventors have a higher maximum temperature of Sc * phase or Sc phase than the above compounds,
As a result of intensive studies on a tolan-based liquid crystal compound useful as a component of the Sc * liquid crystal composition, a novel liquid crystal compound having a structure different from the conventional one was found and the present invention was reached. That is, the present invention is represented by the following general formula

[0005]

[Chemical 2]

[In the formula, R ¹ and R ² represent an alkyl group having 1 to 18 carbon atoms, and A ¹ and A ² are 1,4-phenylene groups optionally substituted by 1 to 2 fluorine atoms. And a liquid crystal composition containing at least one kind of this liquid crystal compound.

In the general formula (1), the alkyl group having 1 to 18 carbon atoms represented by R ¹ and R ² includes (a) straight-chain alkyl group, (b) branched alkyl group, and (c) F (fluorine atom). ) Substituted alkyl group, (d) Cl (chlorine atom)
An alkyl group substituted with, (e) an alkyl group substituted with an alkyloxy group, (f) an optically active alkyl group,
(G) Optically active alkyl group substituted with F (fluorine atom), (h) Optically active alkyl group substituted with Cl (chlorine atom), Optically active alkyl substituted with (ri) alkyloxy group Group, an optically active alkyl group substituted with a (nu) trifluoromethyl group, an optically active alkyl group substituted with a (l) cyano group, and the like. Among these, as specific examples of (a) to (ri), European Patent 0
Alkyl group (R, R ′) described in 385 692
Among them, those having 1 to 18 carbon atoms can be mentioned.

Specific examples of (nu) include the following groups which are optically active: 1-trifluoromethylbutyl group, 1-trifluoromethylpentyl group, 1-trifluoromethylhexyl group, 1- Trifluoromethylheptyl group, 1-trifluoromethyloctyl group, 1-trifluoromethylnonyl group, 1-trifluoromethyldecyl group, 1-trifluoromethylundecyl group, 1-trifluoromethyldodecyl group, 1-tri Fluoromethyl-2-methoxyethyl group, 1-trifluoromethyl-2-ethoxyethyl group, 1-trifluoromethyl-2-propyloxyethyl group, 1-trifluoromethyl-2-butyloxyethyl group, 1-tri Fluoromethyl-2-pentyloxyethyl group, 1-trifluoromethyl-2-hexyloxyethyl group, 1-trifluoromethyl-2-a Propyloxyethyl group, 1-trifluoromethyl-2- (1'-methyl-propyloxy) ethyl, 1-trifluoromethyl -
2- (1'-methylbutyloxy) ethyl group, 1-trifluoromethyl-2- (1'-methylpentyloxy) ethyl group, 1-trifluoromethyl-2- (1'-methylhexyloxy) ethyl group 1-trifluoromethyl-2-
(1'-methylheptyloxy) ethyl group, 1-trifluoromethyl-2- (2'-methylbutyloxy) ethyl group, 1-trifluoromethyl-3-methoxypropyl group,
1-trifluoromethyl-3-ethoxypropyl group, 1-trifluoromethyl-3-propyloxypropyl group, 1-
Trifluoromethyl-3-butyloxypropyl group, 1-
Trifluoromethyl-3-pentyloxypropyl group,
1-trifluoromethyl-3-hexyloxypropyl group, 1-trifluoromethyl-3-isopropyloxypropyl group, 1-trifluoromethyl-3- (1'-methylpropyloxy) propyl group, 1-trifluoromethyl -
3- (1'-methylbutyloxy) propyl group, 1-trifluoromethyl-3- (1'-methylpentyloxy) propyl group, 1-trifluoromethyl-3- (1'-methylhexyloxy) propyl group 1-trifluoromethyl-
3- (1'-methylheptyloxy) propyl group, 1-trifluoromethyl-3- (2'-methylbutyloxy) propyl group, 1-trifluoromethyl-4-methoxybutyl group, 1-trifluoromethyl- 4-ethoxybutyl group, 1-
Trifluoromethyl-4-propyloxybutyl group, 1-
Trifluoromethyl-4-butyloxybutyl group, 1-trifluoromethyl-4-pentyloxybutyl group, 1-trifluoromethyl-4-hexyloxybutyl group, 1-trifluoromethyl-4-isopropyloxybutyl group,
1-trifluoromethyl-4- (1'-methylpropyloxy) butyl group, 1-trifluoromethyl-4- (1'-
Methylbutyloxy) butyl group, 1-trifluoromethyl-4- (1'-methylpentyloxy) butyl group, 1-
Trifluoromethyl-4- (1'-methylhexyloxy) butyl group, 1-trifluoromethyl-4- (1'-methylheptyloxy) butyl group, 1-trifluoromethyl-4- (2'-methylbutyl) (Oxy) butyl group, and the like.

Specific examples of (l) include the following groups, which are optically active: 1-cyanobutyl group, 1-cyanopentyl group, 1-cyanohexyl group, 1-cyanoheptyl group,
Examples thereof include a 1-cyanooctyl group, a 1-cyanononyl group, a 1-cyanodecyl group, a 1-cyanoundecyl group and a 1-cyanododecyl group.

Of those exemplified in (a) to (l), preferred are alkyl groups having 1 to 14 carbon atoms.

The 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms represented by A ¹ and A ² includes 1,4-phenylene group and 2-fluoro-1,4-phenylene group. Group, 3-fluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group and the like.

Specific examples of the liquid crystal compound of the present invention include compounds having groups shown in Tables 1 to 7.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

[0019]

[Table 7]

In Table 1, each symbol represents the following groups (provided that C * represents an asymmetric carbon atom in the following groups). Ph; Chemical 3 PhF; Chemical 4 FPh; Chemical 5 FPhF; Chemical 6

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

The compound contained in the general formula (1) can be synthesized, for example, by the following steps [R ¹ and R ^{2 in the following} formula:
Is the same as in the case of the general formula (1)].

(I) When A ¹ and A ² are 1,4-phenylene groups

[0027]

[Chemical 7]

That is, by reacting halogenobenzene with an acid chloride represented by the general formula (3) in the presence of a Lewis acid (eg, aluminum chloride), the general formula (4)
Can be obtained. The compound represented by the general formula (4) and the compound represented by the general formula (5) are mixed in an inert gas atmosphere,
By reacting with a palladium catalyst, the compound of the general formula (1a), which is the compound of the present invention, can be obtained.

Alternatively, it can be synthesized through the following steps.

[0030]

[Chemical 8]

That is, a compound of the general formula (4) can be obtained by reacting 4-halogenobenzonitrile with a Grignard reagent represented by the general formula (7) and then treating with an acid. A compound of the general formula (1a), which is a compound of the present invention, is obtained by reacting a compound of the general formula (4) with a compound of the general formula (5) under an inert gas atmosphere using a palladium catalyst. You can

Further, the compound represented by the general formula (5) is
It can be synthesized through the following steps.

[0033]

[Chemical 9]

That is, 4-halogenophenol is added to an alkylating agent (for example, an alkyl halide) in the presence of a base.
The compound of the general formula (10) can be obtained by reacting with. Compound of general formula (10) and 3-methyl-
The compound of general formula (11) obtained by reacting 1-butyn-3-ol with a palladium catalyst in an inert gas atmosphere is treated with sodium hydroxide to give a compound of general formula (5). Obtainable.

(II) When A ¹ is a 2-fluoro-1,4-phenylene group and A ² is a 1,4-phenylene group

[0036]

[Chemical 10]

That is, a compound of the general formula (13) is obtained by reacting a compound of the general formula (12) obtained by halogenating m-fluorophenol with an alkylating agent (for example, an alkyl halide) in the presence of a base. Can be obtained. The compound of the general formula (14) obtained by reacting the compound of the general formula (13) with 3-methyl-1-butyn-3-ol using a palladium catalyst in an inert gas atmosphere is treated with sodium hydroxide. By the general formula (15)
Can be obtained. By reacting the compound of general formula (15) with the compound of general formula (4) using a palladium catalyst in an inert gas atmosphere, the compound of general formula (1b), which is the compound of the present invention, can be obtained. .

(III) When A ¹ is a 3-fluoro-1,4-phenylene group and A ² is a 1,4-phenylene group

[0039]

[Chemical 11]

That is, a compound of the general formula (17) is obtained by reacting a compound of the general formula (16) obtained by halogenating o-fluorophenol with an alkylating agent (eg alkyl halide) in the presence of a base. Can be obtained. The compound of general formula (18) obtained by reacting the compound of general formula (17) with 3-methyl-1-butyn-3-ol using a palladium catalyst in an inert gas atmosphere is treated with sodium hydroxide. Then, the general formula (19)
Can be obtained. A compound of the general formula (1c), which is a compound of the present invention, can be obtained by reacting the compound of the general formula (19) with the compound of the general formula (4) under an inert gas atmosphere using a palladium catalyst. . (Iv) When A ¹ is a 2,3-difluoro-1,4-phenylene group and A ² is a 1,4-phenylene group

[0041]

[Chemical 12]

That is, a compound of the general formula (20) obtained by reacting 2,3-difluorophenol with an alkylating agent (for example, an alkyl halide) in the presence of a base is iodinated with periodic acid and iodine. By doing so, the compound of the general formula (21) can be obtained. General formula (2
By treating the compound of the general formula (22) obtained by reacting the compound of 1) with 3-methyl-1-butyn-3-ol with a palladium catalyst in an inert gas atmosphere, by treating with sodium hydroxide. A compound of the general formula (23) can be obtained. By reacting the compound of general formula (23) with the compound of general formula (4) using a palladium catalyst in an inert gas atmosphere, the compound of general formula (1)
The compound of d) can be obtained. (V) A ¹ is a 1,4-phenylene group and A ² is 2-fluoro-
In case of 1,4-phenylene group

[0043]

[Chemical 13]

That is, 2-fluoro-4-halogenophenol is treated with copper (I) cyanide and then reacted with benzyl chloride in the presence of a base to obtain 4-benzyloxy-3-fluorobenzonitrile. You can
After reacting 4-benzyloxy-3-fluorobenzonitrile with the Grignard reagent represented by the general formula (7),
The compound of general formula (24) can be obtained by treating with an acid. After hydrolyzing the compound of the general formula (24) using 5% palladium carbon, by reacting trifluoromethanesulfonic anhydride,
The compound of the general formula (26) can be obtained. By reacting the compound of general formula (26) with the compound of general formula (5) using a palladium catalyst in an inert gas atmosphere, the compound of general formula (1e), which is the compound of the present invention, can be obtained. . (VI) A ¹ is a 1,4-phenylene group, A ² is 3-fluoro-
In case of 1,4-phenylene group

[0045]

[Chemical 14]

That is, after treating 3-fluoro-4-halogenophenol with copper (I) cyanide and then reacting with benzyl chloride in the presence of a base, 4-benzyloxy-2-fluorobenzonitrile is obtained. You can
After reacting 4-benzyloxy-2-fluorobenzonitrile with the Grignard reagent represented by the general formula (7),
The compound of general formula (27) can be obtained by treating with an acid. By hydrolyzing the compound of the general formula (27) using 5% palladium carbon, and then reacting with trifluoromethanesulfonic anhydride,
A compound of general formula (29) can be obtained. By reacting the compound of general formula (29) with the compound of general formula (5) using a palladium catalyst in an inert gas atmosphere, the compound of general formula (1f), which is the compound of the present invention, can be obtained. . (VII) When A ¹ is a 1,4-phenylene group and A ² is a 2,3-difluoro-1,4-phenylene group

[0047]

[Chemical 15]

That is, 4-benzyloxy-2,3-difluorobenzonitrile is reacted with a Grignard reagent represented by the general formula (7) and then treated with an acid to obtain a compound of the general formula (30). be able to. The compound of general formula (30) can be obtained by hydrolyzing the compound of 5% palladium carbon and then reacting it with trifluoromethanesulfonic anhydride. By reacting the compound of general formula (32) with the compound of general formula (5) using a palladium catalyst in an inert gas atmosphere, a compound of general formula (1g), which is a compound of the present invention, can be obtained. .

4-Benzyloxy-2,3-difluorobenzonitrile can be synthesized through the following steps.

[0050]

[Chemical 16]

That is, 1-benzyloxy-2,3-difluorobenzene obtained by reacting 2,3-difluorophenol with benzyl chloride in the presence of a base was lithiated with n-butyllithium, 4-Benzyloxy-2,3-difluorobenzoic acid can be obtained by reacting with carbon dioxide gas. 4-benzyloxy-
4-Benzyloxy-2,3-difluorobenzonitrile can be obtained by treating 2,3-difluorobenzoic acid with thionyl chloride, reacting it with ammonia, and dehydrating it with thionyl chloride.

The liquid crystal compound is generally used as a component of a liquid crystal composition composed of two or more kinds of components, and the liquid crystal compound of the present invention can also be used as a component of the liquid crystal composition. The liquid crystal composition of the present invention comprises a mixture of a plurality of compounds and contains at least one liquid crystal compound of the present invention. Examples of the composition of the present invention include the liquid crystal composition [1] of the present invention exhibiting the Sc phase and the liquid crystal composition [2] of the present invention exhibiting the Sc * phase.

In the liquid crystal composition [1] of the present invention, at least one inactive liquid crystal compound of the present invention is contained as an essential component, and as an optional component, another liquid crystal compound (2-
4'-alkyloxyphenyl-5-alkylpyrimidine, 2-4'-alkylphenyl-5-alkyloxypyrimidine, 2-4'-alkyloxyoxyphenyl-5-alkyloxypyrimidine, 2-p-alkyloxycarbonylphenyl -5-alkylpyrimidine, 2-4'-alkyloxy-3'-fluorophenyl-5-alkylpyrimidine, 2-4'-alkyloxy-2 ', 3'-difluorophenyl-5-alkylpyrimidine, 2-4 '-Alkyloxyphenyl-5-alkylpyridine, 2-4'-alkyloxy-3'-fluorophenyl-5-alkylpyridine, etc.), a smectic liquid crystal compound not exhibiting an Sc phase and a liquid crystal compound exhibiting a nematic phase It is a mixture containing compounds. In the liquid crystal composition [1] of the present invention, the content of one or more liquid crystal compounds of the present invention is usually 5 to 100% by weight.

The liquid crystal composition [2] of the present invention contains at least one kind of the optically active liquid crystal compound of the present invention as an essential component,
As an optional component, the liquid crystal composition [1] of the present invention, another liquid crystal compound showing a Sc phase (2-4′-alkyloxyphenyl-
5-alkylpyrimidine, 2-4'-alkylphenyl-5
-Alkyloxypyrimidine, 2-4'-alkyloxyoxyphenyl-5-alkyloxypyrimidine, 2-p-
Alkyloxycarbonylphenyl-5-alkylpyrimidine, 2-4'-alkyloxy-3'-fluorophenyl
-5-alkylpyrimidine, 2-4'-alkyloxy-
2 ', 3'-difluorophenyl-5-alkylpyrimidine, 2-4'-alkyloxyphenyl-5-alkylpyridine, 2-4'-alkyloxy-3'-fluorophenyl-5-alkylpyridine, etc., Sc * Liquid crystal compound showing phase (optically active 4-alkyloxy-4'-biphenylcarboxylic acid-p '-(2-methylbutyloxycarbonyl) phenyl ester, optically active 4-n-alkyloxy-4'-
Biphenylcarboxylic acid-2-methylbutyl ester, etc.),
Chiral compound (Japanese Patent Laid-Open No. 63-99032, Japanese Patent Laid-Open No. 63-99032)
-190843, JP-A-2-138274, JP-A-2-
256673, JP-A-2-262579, JP-A-2-2
86673, compounds described in JP-A-3-27374, etc.), smectic liquid crystal compounds showing no Sc phase, liquid crystal compounds showing nematic phase, and compounds selected from dichroic dyes (anthraquinone dyes, azo dyes, etc.). It is a mixture containing. In the liquid crystal composition [2] of the present invention, the content of one or more liquid crystal compounds of the present invention is usually 5 to 100% by weight.

A liquid crystal composition exhibiting ferroelectricity causes an optical switching phenomenon when a voltage is applied, and a liquid crystal display element having a fast response can be manufactured by utilizing this phenomenon [eg, Japanese Patent Laid-Open No. 56-1].
07216, JP 59-118744, NA Clark, Estila Ragawall (STL
agerwall) ； Applied Physics Letter (Appli
ed Physics Letter) 36, 899 (1980), etc.].

Liquid crystal composition of the present invention [2] showing the Sc * phase
Can be used as an optical switching element (liquid crystal display element) by vacuum-sealing in a liquid crystal cell having a cell interval of 0.5 to 10 μm, preferably 0.5 to 3 μm and installing polarizers on both sides. The above liquid crystal cell can be produced by providing a transparent electrode and bonding two glass substrates, the surfaces of which are aligned, with a spacer interposed therebetween. Examples of the spacer include alumina beads, glass fiber, and polyimide film. As the alignment treatment method, a normal alignment treatment, such as a rubbing treatment of a polyimide film or an oblique SiO vapor deposition, can be applied.

[0057]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 No. 1 in Table 1 Preparation of compound 12 4-iodo-n-decyloxybenzene (this compound can be obtained by reacting 4-iodophenol with n-decyl bromide in the presence of a base) 2
7.8 g (77.2 mmol) and 3-methyl-1-butyn-3-ol 7.8
g (92.9 mmol) in 200 ml of triethylamine, 270 m of dichlorobistriphenylphosphine palladium (II) as a catalyst
g (0.39 mmol) and 68 mg (0.36 mmol) of copper (I) iodide were reacted under a nitrogen atmosphere at room temperature for 5 hours. After completion of the reaction, triethylamine was distilled off and the mixture was extracted with hexane.
The hexane layer was washed with 1N hydrochloric acid and water, and then hexane was distilled off. 300 ml of dry toluene and 2.8 g (70.0 mmol) of powdery sodium hydroxide were added to the obtained liquid, and the mixture was heated under reflux for 1 hour. After cooling, the toluene layer was washed with water and the toluene was distilled off to obtain 13.1 g (50.8 mmol) of oily 4-n-decyloxyphenylacetylene. 1.4 g (58.3 mmol) of magnesium metal, 5.0 g (27.9 mmol) of optically active 4-methyl-1-bromohexane and 1,2
-To 30 ml of a dry ether solution of Grignard reagent prepared from 5.3 g (28.2 mmol) of dibromoethane, dry benzene 12
0 ml and 4.1 g (22.5 mmol) of 4-bromobenzonitrile were added, and the mixture was heated under reflux for 5 hours. The reaction solution was cooled to 10 ° C or lower, 20 ml of 6N hydrochloric acid was added, and the mixture was heated under reflux for 6 hours. After cooling, the organic layer was washed and the solvent was distilled off. By recrystallizing the obtained solid from methanol, the optically active 4- (4-
Methylhexylcarbonyl) bromobenzene 3.8 g (13.4
mmol) was obtained. 2.6 g of 4-n-decyloxyphenylacetylene obtained in
(10.0 mmol) and optically active 4- (4-methylhexylcarbonyl) bromobenzene 2.8 g (10.0 mmol) in 80 ml triethylamine, dichlorobistriphenylphosphine palladium (II) 36 mg (0.05 mmol), iodide Copper (I) 9mg (0.05mmol) and triphenylphosphine
72 mg (0.27 mmol) was used and it heated and refluxed for 8 hours under nitrogen atmosphere. After completion of the reaction, triethylamine was distilled off and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid and water, purified with a silica gel column, and recrystallized three times from methanol to give the compound of the present invention, No. 1 in Table 1. 12
1.9 g (4.1 mmol) of the compound of The structure of the compound is N
Confirmed by MR (nuclear magnetic resonance spectrum analysis), MS (mass spectrometry), IR (infrared absorption spectrum analysis) and elemental analysis. IR (cm ^-1 ) 2922.0 2854.0 2218.0 1682.0 1601.0 1518.0 1470.0 1406.0 1292.0 1259.0 1139.0 826.0 NMR (ppm) 0.72-0.90 (m, 9H) 1.10-1.73 (m, 23H) 2.91 (t, 2H) 3.95 (t, 2H) 6.87 (d, 2H) 7.46 (d, 2H) 7.57 (d, 2H) 7.91 (d, 2H) Elemental analysis value Theoretical value (%) Actual value (%) C: 83.43 C: 83.25 H: 9.63 H: 9.72

Example 2 No. 1 in Table 1 Production of Compound 11 The same operation as in Example 1 except that optically active 2-methyl-1-bromobutane was used in the same molar ratio in place of optically active 4-methyl-1-bromohexane in Example 1. By performing the procedure described above, optically active 4- (2-methylbutylcarbonyl) bromobenzene was obtained. Optically active 4- (2-methylbutylcarbonyl) obtained in
By reacting bromobenzene and 4-n-decyloxyphenylacetylene obtained in Example 1 in the same molar ratio as in Example 1 under the same conditions, No. 1 in Table 1 which is a compound of the present invention. 11 compounds were obtained. IR (cm ^-1 ) 2920.0 2854.0 2218.0 1686.0 1597.0 1516.0 1284.0 1247.0 1031.0 830.0 NMR (ppm) 0.73 to 0.97 (m, 9H) 1.22 to 1.50 (m, 16H) 1.72 to 1.83 (m, 2H) 2.00 to 2.15 (m, 1H) 2.72 (dd, 1H) 2.93 (dd, 1H) 3.96 (t, 2H) 6.83 (d, 2H) 7.46 (d, 2H) 7.57 (d, 2H) 7.91 (d, 2H) Elemental analysis value Theoretical value ( Actual value (%) C: 83.28 C: 83.01 H: 9.32 H: 9.45

Example 3 No. 3 in Table 3 Preparation of Compound 52 To a suspension of 20.0 g of n-decanoic acid chloride and 14.7 g of aluminum chloride in 50 ml of chloroform was added 20 ml of a chloroform solution of 22.5 g of 4-iodobenzene at 10 ° C or lower, and the mixture was stirred at room temperature for 6 hours. The chloroform layer was washed with water and chloroform was distilled off. By recrystallizing the obtained solid from methanol, 4-n-nonylcarbonyl-iodobenzene 15.
I got 0g. In Example 1, 2-fluoro-4-iodo-n-nonyloxybenzene was used instead of 4-iodo-n-decyloxybenzene (this compound was prepared by iodizing 2-fluorophenol with iodine). , In the presence of a base, n
-Can be obtained by reacting with nonyl bromide) was used in the same molar ratio to obtain 3-fluoro-4-n-nonyloxyphenylacetylene. . 4-n-nonylcarbonyl-iodobenzene obtained in Step 3.6
2.6 g (10.0 mmol) of 3-fluoro-4-n-nonyloxyphenylacetylene obtained with g (10.0 mmol) in 80 ml of triethylamine, 36 mg (0.05 mmol) of dichlorobistriphenylphosphine palladium (II) as a catalyst and iodinated 6 mg of copper (I) at room temperature under nitrogen atmosphere with 6 mg (0.05 mmol)
Reacted for hours. After completion of the reaction, triethylamine was distilled off and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid and water, purified with a silica gel column, and recrystallized from methanol three times to give N in Table 3 as a compound of the present invention.
o. 2.6 g (5.3 mmol) of the compound of 52 were obtained. IR (cm ^-1 ) 2920.0 2852.0 1682.0 1601.0 1520.0 1466.0 1276.0 1207.0 1106.0 878.0 816.0 NMR (ppm) 0.83 to 0.91 (m, 6H) 1.18 to 1.86 (m, 28H) 2.92 (t, 2H) 4.03 (t, 2H) 6.91 (t, 1H) 7.22 to 7.28 (m, 2H) 7.57 (d, 2H) 7.92 (d, 2H) ¹⁹ F-NMR -58.30 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C : 80.44 C: 80.29 H: 9.21 H: 9.30 F: 3.86 F: 3.75

Example 4 In Table 3, No. Preparation of Compound 56 In Example 1, 2-fluoro-4-iodo-n-decyloxybenzene was used instead of 4-iodo-n-decyloxybenzene (this compound uses 2-fluorophenol and iodine. And iodinated, then in the presence of a base, n
-Can be obtained by reacting with -decyl bromide) was used in the same molar ratio to obtain 3-fluoro-4-n-decyloxyphenylacetylene. . The 3-fluoro-4-n-decyloxyphenylacetylene obtained in Example 1 was reacted with the optically active 4- (4-methylhexylcarbonyl) bromobenzene obtained in Example 1 in the same molar ratio as in Example 1 under the same conditions. No. in Table 3 which is a compound of the present invention. 56 compounds are obtained. IR (cm ^-1 ) 2928.0 2216.0 1680.0 1603.0 1520.0 1468.0 1301.0 1276.0 1243.0 1207.0 1106.0 982.0 878.0 816.0 420.0 NMR (ppm) 0.82 to 0.91 (m, 9H) 1.05 to 1.88 (m, 23H) 2.92 (t, 2H) 4.03 (t , 2H) 6.90 (t, 1H) 7.21 to 7.28 (m, 2H) 7.58 (d, 1H) 7.92 (d, 1H) ¹⁹ F-NMR -58.31 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 80.29 C: 80.01 H: 9.05 H: 9.10 F: 3.97 F: 4.11

Example 5 In Table 4, No. Preparation of compound 74. In Example 1, instead of 4-iodo-n-decyloxybenzene, 2,3-difluoro-4-iodo-n-
Same as nonyloxybenzene (this compound can be obtained by reacting 2,3-difluorophenol with n-nonyl bromide in the presence of a base, and then iodinated with periodate and iodine) By performing the same operation as in Example 1 except that the molar ratio was used,
2,3-difluoro-4-n-nonyloxyphenylacetylene was obtained. Reacting 2,3-difluoro-4-n-nonyloxyphenylacetylene obtained in Example 4 with 4-n-nonylcarbonyl-iodobenzene obtained in Example 3 in the same molar ratio as in Example 3 and under the same conditions. No. in Table 4 which is the compound of the present invention. 74 compounds are obtained. IR (cm ^-1 ) 2920.0 2854.0 2210.0 1686.0 1601.0 1518.0 1470.0 1301.0 1083.0 NMR (ppm) 0.87 to 0.95 (m, 6H) 1.16 to 1.51 (m, 24H) 1.65 to 1.88 (m, 4H) 2.95 (t, 2H) 4.06 (t, 2H) 6.67 to 6.75 (m, 1H) 7.15 to 7.23 (m, 1H) 7.59 (d, 2H) 7.94 (d, 2H) ¹⁹ F-NMR -82.64 (dd, 1F) -57.63 (dd, 1F ) Elemental analysis value Theoretical value (%) Actual value (%) C: 77.65 C: 77.53 H: 8.63 H: 8.39 F: 7.45 F: 7.61

Example 6 In Table 4, No. Preparation of the compound of 78 In Example 1, instead of 4-iodo-n-decyloxybenzene, 2,3-difluoro-4-iodo-n-
Decyloxybenzene (this compound can be obtained by reacting 2,3-difluorophenol with n-decyl bromide in the presence of a base, followed by iodination with periodic acid and iodine) By performing the same operation as in Example 1 except that the molar ratio was used,
2,3-difluoro-4-n-decyloxyphenylacetylene was obtained. The 2,3-difluoro-4-n-decyloxyphenylacetylene obtained in Example 1 was reacted with 4- (4-methylhexylcarbonyl) bromobenzene obtained in Example 1 in the same molar ratio as in Example 1 under the same conditions. No. in Table 4 which is a compound of the present invention. 78 compounds are obtained. IR (cm ^-1 ) 2926.0 2210.0 1680.0 1603.0 1520.0 1481.0 1408.0 1305.0 1083.0 799.0 NMR (ppm) 0.81 to 0.92 (m, 9H) 1.05 to 1.50 (m, 19H) 1.60 to 1.88 (m, 4H) 2.93 (t, 2H) 4.06 (t, 2H) 6.68 ~ 6.75 (m, 1H) 7.15 ~ 7.22 (m, 1H) 7.59 (d, 2H) 7.94 (d, 2H) ¹⁹ F-NMR -82.64 (dd, 1F) -57.64 (dd, 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 77.42 C: 77.53 H: 8.47 H: 8.49 F: 7.66 F: 7.43

Example 7 No. in Table 7 Preparation of the compound of 140 2,3-difluoro-benzyloxybenzene (this compound can be obtained by reacting 2,3-difluorophenol with benzyl chloride in the presence of a base) 24.1 g and N, N, 25.4 g of N ′, N′-tetramethylethylenediamine was dissolved in 200 ml of dry tetrahydrofuran and cooled to −60 ° C. or lower with a dry ice-acetone bath. Add to this a solution of n-butyllithium in hexane (15
%) 74 ml was added dropwise at -55 ° C or lower, and the mixture was stirred for 3 hours as it was, and then carbon dioxide gas was blown at -55 ° C or lower. After completion of the reaction, tetrahydrofuran was distilled off, 1N hydrochloric acid was added, and the insoluble matter was collected by filtration. By recrystallizing this from toluene, 2,3-difluoro-4-benzyloxybenzoic acid 15.
I got 1g. 20 ml of thionyl chloride was added to 15.1 g of 2,3-difluoro-4-benzyloxybenzoic acid obtained in (3), and the mixture was heated under reflux for 6 hours. Excess thionyl chloride was removed, the obtained solid was dissolved in 150 ml of dry toluene, and ammonia gas was blown into this at 10 ° C. or lower. The precipitated solid was collected by filtration to obtain 14.4 g of 2,3-difluoro-4-benzyloxybenzamide. 50 ml of thionyl chloride was added to 14.4 g of 2,3-difluoro-4-benzyloxybenzamide obtained in the above, and the mixture was heated under reflux for 12 hours. Excess thionyl chloride was removed and the resulting solid was extracted with toluene. The toluene layer was washed with water, toluene was distilled off, and the obtained solid was recrystallized from hexane to obtain 8.0 g of 2,3-difluoro-4-benzyloxybenzonitrile. To 20 ml of a dry ether solution of Grignard reagent prepared from 0.83 g of metallic magnesium, 3.6 g of n-nonyl bromide and 3.3 g of 1,2-dibromoethane, 80 ml of dry benzene
2.1 g of 2,3-difluoro-4-benzyloxybenzonitrile obtained in and were added, and the mixture was heated under reflux for 5 hours. The reaction solution was cooled to 10 ° C. or lower, 10 ml of 6N hydrochloric acid was added, and the mixture was heated under reflux for 6 hours. After cooling, the organic layer was washed and the solvent was distilled off. By recrystallizing the obtained solid from methanol, 2.1 g of 2,3-difluoro-4-n-nonylcarbonyl-benzyloxybenzene was obtained. 2,3-difluoro-4-n-nonylcarbonyl obtained in
-2.1 g of benzyloxybenzene was hydrolyzed at room temperature in a hydrogen atmosphere in ethanol using 0.5 g of 5% palladium carbon. After confirming that the absorption of hydrogen disappeared, the catalyst was removed by filtration and ethanol was distilled off. By recrystallizing the obtained solid from hexane,
1.3 g of -difluoro-4-n-nonylcarbonylphenol was obtained. 1.3 g of 2,3-difluoro-4-n-nonylcarbonylphenol obtained in step 1 was dissolved in 30 ml of dry pyridine, and
Trifluoromethanesulfonic anhydride 1.4 below 0 ° C
g was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, the mixture was poured into ice water and extracted with toluene. The toluene layer was washed successively with 1N hydrochloric acid, water, aqueous sodium hydrogencarbonate and water, and the toluene was distilled off to give an oily 2,3-difluoro-
1.5 g of 4-n-nonylcarbonylphenol-trifluoromethanesulfonic acid ester was obtained. In Example 1, 4-iodo-n-decyloxybenzene was replaced with 4-iodo-n-nonyloxybenzene (this compound reacts 4-iodophenol with n-nonyl bromide in the presence of a base). The same operation as in Example 1 was carried out to obtain 4-n-nonyloxyphenylacetylene. 2,3-Difluoro-4-n-nonylcarbonylphenol-trifluoromethanesulfonic acid ester obtained in 1.5
4-n-nonyloxyphenylacetylene obtained with g 0.9
In 30 ml of triethylamine, 12 mg of dichlorobistriphenylphosphine palladium (II), 4 mg of copper (I) iodide and 24 mg of triphenylphosphine were used as catalysts and heated under reflux for 8 hours in a nitrogen atmosphere. After completion of the reaction, triethylamine was distilled off and the mixture was extracted with toluene. The toluene layer was washed with 1N hydrochloric acid and water, purified with a silica gel column, and recrystallized from methanol three times to give No. 0.8 g of 140 compounds are obtained. IR (cm ^-1 ) 2920.0 2852.0 2210.0 1684.0 1603.0 1518.0 1460.0 1253.0 820.0 NMR (ppm) 0.82 to 0.95 (m, 6H) 1.17 to 1.50 (m, 2H) 1.65 to 1.85 (m, 4H) 2.90 to 3.00 (m, 2H ) 3.97 (t, 2H) 6.88 (d, 2H) 7.25 ~ 7.32 (m, 1H) 7.49 (d, 2H) 7.52 ~ 7.60 (m, 1H) ¹⁹ F-NMR -59.94 (dd, 1F) -58.92 (dd , 1F) Elemental analysis value Theoretical value (%) Actual value (%) C: 77.65 C: 77.70 H: 8.63 H: 8.57 F: 7.45 F: 7.41

Example 8 Compounds of Example 1, Example 2 and Example 5 (N in Table 1)
o. 12, No. 12 in Table 1. 11 and No. 11 in Table 4. No. 74 compound) and the compounds shown in Chemical formulas 17 to 37 below.
The liquid crystal composition of the present invention was obtained by mixing in the proportions shown in.

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

[0075]

[Chemical 27]

[0076]

[Chemical 28]

[0077]

[Chemical 29]

[0078]

[Chemical 30]

[0079]

[Chemical 31]

[0080]

[Chemical 32]

[0081]

[Chemical 33]

[0082]

[Chemical 34]

[0083]

[Chemical 35]

[0084]

[Chemical 36]

[0085]

[Chemical 37]

Chemical formula 17 to chemical formula 20 and chemical formula 28 to chemical formula 2
In 9 NAP is a 2,6-naphthylene group
In Chemical formula 37, C * represents an asymmetric carbon atom.

[0087]

[Table 8]

This liquid crystal composition was applied to polyimide as an alignment treatment agent, and the surface was rubbed to be injected into a cell having a cell thickness of 2 μm provided with a transparent electrode which was subjected to antiparallel treatment to form an optical switching element. This element was placed between two orthogonal polarizers, and the response speed when a voltage of ± 10 V was applied was measured and found to be 61 μsec at 25 ° C. The orientation was uniform without zigzag defects.

Table 9 shows the phase transition temperatures of the compounds and compositions obtained in Examples 1 to 8.

[0090]

[Table 9]

Each symbol in Table 9 has the following meaning. Cry; Crystal phase S ₁ ; Unidentified smectic phase Sc *; Chiral smectic C phase Sc; Smectic C phase S _A ; Smectic A phase Iso; Isotropic liquid phase ・; Phase exists (); Represents monotropic phase -; Phase does not exist <RT; below room temperature

[0092]

By using the liquid crystal compound of the present invention as a component of the Sc * liquid crystal composition, a Sc * liquid crystal composition having a relatively high maximum temperature of the Sc * phase can be obtained. Therefore, the compounds and compositions of the present invention are useful as liquid crystal materials used in liquid crystal display devices.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuro Yanagi 1 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd.

Claims (2)

[Claims] 1. The following general formula: [In the formula, R ¹ and R ² represent an alkyl group having 1 to 18 carbon atoms, and A ¹ and A ² represent a 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms] A liquid crystal compound represented by. 2. A liquid crystal composition comprising a mixture of a plurality of compounds and containing at least one liquid crystal compound according to claim 1.