JPH03218352A - Pyridine liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R, R' are 1-18C alkyl; X<1> is direct bond, O, S, CidenticalC; A<1>, A<3> are 1,4-phenylene which may be substituted with one- four F or Cl atoms; (n) is 0, 1; X<2> is CidenticalC, CH2CH2; A<2> is formula II or III; X<3> is direct bond, O, S; but when (n) is O and A<2> is formula II, X<1> is CidenticalC). USE:A smectic C liquid crystal. Useful as a component for changing the dielectric anisotropy of a liquid crystal into a negative state and also as a component for enlarging the temperature range of the smectic C phase. The compound is stable against light, heat and water and has excellent compatibility with other smectic liquid crystals. PREPARATION:For example, a compound of formula IV (Y is Br, I) is subjected to a reaction with an alkylating agent in the presence of a base to prepare a compound of formula V, which is converted into a Grignard reagent. The reagent is allowed to react with a 2,5-dihalogenopyridine and the prepared compound of formula VI is further made to react in the presence of a Pd catalyst in triethylamine to provide a compound of formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid crystal compound useful as a ferroelectric liquid crystal material.

[Conventional technology No. 1 - Currently, TN (twisted nematic) is used as a liquid crystal display element.
The type designation method is the most widely used.

This TN liquid crystal display has many advantages such as low driving voltage and low power consumption. However, they are inferior to light-emitting devices (cathode tubes, electroluminescence, plasma displays, etc.) in terms of response speed. A new TN type display element with a twist angle of 180 to 270 degrees has also been developed, but its response speed is still inferior. Although various efforts for improvement have been made as described above, a TN type display element with a fast response speed has not yet been realized.

However, a new display method using ferroelectric liquid crystals, which has been actively researched recently, has the potential to significantly improve response speed (N. A. Clark et al.;
App! ied Phys. Lett. , 36,
899 (1980)). This method utilizes a chiral smectic phase such as a chiral smectic C phase that exhibits ferroelectricity. Phases that exhibit ferroelectricity are not only chiral smectic C phase, but also chiral smectic F,
It is known that phases such as G and H 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; It is necessary to use a ferroelectric liquid crystal composition obtained by mixing liquid crystal compounds or non-liquid crystal compounds.

In addition to the ferroelectric liquid crystal compositions consisting only of ferroelectric liquid crystal compounds, JP-A-60-36003 discloses compounds exhibiting non-chiral smectic C, F, G, H, I, etc. phases and It has been reported that the composition as a basic substance can be mixed with one or more compounds exhibiting a ferroelectric liquid crystal phase to form a ferroelectric liquid crystal composition as a whole. Furthermore, it has been reported that a compound or composition exhibiting a phase such as smectic C is used as a basic substance, and one or more compounds that are optically active but do not exhibit a ferroelectric liquid crystal phase are mixed to form a ferroelectric liquid crystal composition as a whole. (Mol.Cryst.Liq.Cryst., 8
9, 327 (1982)).

Taken together, it can be seen that a ferroelectric liquid crystal composition can be constructed by mixing one or more optically active compounds with a basic substance, regardless of whether or not they exhibit a ferroelectric liquid crystal phase.

As these basic substances, various compounds such as smectic C which exhibit a non-irradial smectic liquid crystal phase can be used, but for practical purposes, liquid crystal compounds or mixtures which exhibit a smectic C phase in a wide temperature range including room temperature are desirable. Components of these smectic C liquid crystal mixtures include liquid crystal compounds such as phenylbenzoate, biphenyl, phenylpyridine, and 5-alkyl-2-(4-alkoxyphenyl)pyrimidine.

[Problem to be solved by the invention] However, it is unclear whether chiral smectic C liquid materials obtained by adding optically active compounds to these materials exhibit excellent performance in liquid crystal displays that utilize ferroelectricity. A final evaluation has not yet been obtained. This is because liquid crystal displays that utilize ferroelectricity have not yet been technically perfected. Therefore, it is currently necessary to test various new smectic C-4 materials.

[Means for Solving the Problems] The present inventors have conducted extensive studies on novel liquid crystal compounds exhibiting a smectic C phase that are suitable for use in the above-mentioned applications, and as a result, have arrived at the present invention. That is, the present invention provides general formula R-X'-(-A'-X"-)n-A"-A3-X3-
R' (1) [wherein R, R' are alkyl groups having 1 to 18 carbon atoms, X1 is a direct bond, -0-, -S- or -
C≡C-, A1 and A3 are 1,4-phenylene groups optionally substituted with 1 to 4 fluorine atoms or chlorine atoms, n is 0 or 1, x2 is -CEC- or -CH
2CH2-, A2 represents -Q1 or -D-, X3 represents a direct bond, 10- or -S- (provided that n is O, A
If 2 is -Q-(7), then X1 is -(,"C-))
It is a pyridine-based liquid crystal compound represented by

In general formula (1), R, R' have 1 to 18 carbon atoms
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-hebutyl group, n-octyl-5yl group, n-nonyl group. group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, etc.

Among these, preferably an alkyl group having 4 to 14 carbon atoms.

A1 and A3 are preferably 1,4-phenylene groups optionally substituted with 1 to 2 fluorine atoms.

X3 is preferably a direct bond and 10-.

As a specific example of the compound represented by the general formula (1), Table-
Examples include compounds having groups as shown in 1.

16- (I) When n is 1.

Table-1 (1) -7- Table-1 (2) -8- Table-1 (3) -9- Table-1 (4) -10- Table-1 (5) Table-1 (6) Table-1 (7) -131 Table-1 (8) -14- Table-1 (9) (II) n is 1, When X2 is -C≡C- and A2 is 10-.

Table-1 (10) Table-1 (11) Table-1 (12) (m) n is 1, X2 is -CH2CH2-, A2 is 10-
in the case of.

Table-1 (13) =17- Table-1 (14) -18- Table-1 (15) In Table-1, BUT PEN 11EX 11EP OCT NON DEC UND D.O.D. TED Ac ? Each symbol represents the following group.

n-C4}1g - n-C5 t{1 1 - n-C6 H1 3 - n-C7 H15 - n-CBH. ■1n-Cg ■1g - n-c1s}I2t- n-C,1 1{23- n1012H25- n-C1,tl2g- -C≡C- Compounds included in single bond general formula (1) can be synthesized, for example, through the following steps [in the following formula, R, R', X' and X3
is the same as in general formula (1)].

■ n is 0, x1 is -C≡C-, A2 is -O-, A3 is -21- In other words, the compound of general formula (2) is treated with an alkylating agent (e.g. and alkyl halide) to obtain a compound of general formula (4).

After the compound of general formula (4) is treated with metallic magnesium to form a Grignard reagent, 2,5-dihalogenopyridines (e.g. 2,5- The compound of general formula (6) and the compound of general formula (7) are reacted with zero- or divalent palladium in triethylamine under an inert gas atmosphere. By carrying out the reaction using a catalyst, the compound of general formula (1a), which is the compound of the present invention, can be obtained.

■ n is o, x' is a direct bond, A2 is -D-, A3 is Y"-(:)-NO2 (Y"; Cl, Bro or) (8) R"-CmiC-Q-NO2 ( 10) R-Q-V" (13) In triethylamine under inert gas atmosphere, O value or 2
The compound of general formula (10) is obtained by reaction using a valent palladium catalyst.

The compound of general formula (10) in the presence of palladium carbon,
A compound of general formula (11) is obtained by hydrogenation.

The compound of general formula (11) is induced to a diazonium salt by the action of sodium nitrite, and then reacted with potassium halide to obtain the compound of general formula (13).

By reacting the compound of general formula (8) with metallic magnesium to form a Grignard reagent, and then reacting it with the compound of general formula (13) in an inert gas atmosphere in the presence of a zero- or divalent palladium or nickel catalyst. , a compound of general formula (1b), which is a compound of the present invention, can be obtained.

-25-(Y"; Cl, Br or I) -26- That is, the compound of general formula (14) and 3-methyl-1-butyn-3-ol are mixed with zero or divalent palladium under an inert gas atmosphere. A compound of general formula (16) is obtained by reacting with a catalyst and then treating with sodium hydroxide.

By reacting the compound of general formula (6') and the compound of general formula (16) in an inert gas atmosphere using a zero-valent or divalent palladium catalyst, the compound of the general formula ( IC) can be obtained.

In addition, in the synthesis method of the compound of general formula (6'), x3 is -O
In the case of -, the method for synthesizing the compound of general formula (6) is followed. X
When 3 is a direct bond, it can be synthesized, for example, through the following steps.

R'-0-Nll2 (17) R'-0-Y" (18) That is, by reacting the compound of general formula (11) with sodium nitrite to induce it into a diazonium salt, and then reacting it with potassium halide. A compound of general formula (18) is obtained.

After treating the compound of general formula (18) with metallic magnesium to form a Grignard reagent, in an inert gas atmosphere in the presence of a zero-valent or divalent palladium or nickel catalyst,
By reacting with 2,5-dihalogenopyridines (e.g. 2,5-dibromopyridine), general formula (6'')
can be obtained.

-29- That is, the compound of general formula (1d), which is a compound of the present invention, can be obtained by hydrogenating the compound of general formula (1c) in the presence of palladium carbon.

Liquid crystals are generally used as liquid crystal compositions consisting of two or more components, and the liquid crystal compound of the present invention can also be used as a component of liquid crystal compositions. The liquid crystal composition includes smectic liquid crystals, such as smectic liquid crystals that do not have optically active sites [2-p-alkyloxyphenyl-5-alkylpyrimidine, 2-p-alkylphenyl-5-alkyloxyvirimicin, 2- p-alkanoyloxyphenyl-5-alkylpyrimidine, 2-p-alkyloxylphenyl-5-alkylpyrimidine, 2-
p-alkylphenyl-5-p-alkyloxyphenylpyrimidine, 2-p-alkyloxy-m-fluorophenyl-5-alkylpyrimidine, 2-p-alkyl-30-monoxyphenyl-5- (trans- 4-alkylcyclohexyl)pyrimidine, 2-p-alkyloxyphenyl-5-alkylpyridine, 2-p-alkyloxy-m-fluorophenyl-5-alkylpyridine, 2
-p- (p'-alkylphenyl)phenyl-5-alkylpyrimidine, 2-p-alkylphenyl-5-p
-alkylphenylpyrimidine, p-alkyloxyphenyl-5-alkyl picolinate, 2-p-alkyloxyphenyl-5-alkyloxypyrazine, 2-p
-alkylphenyl-5-alkylpyrimidine, 2-p
-Alkyloxyphenyl-5-alkyloxypyrimicin, 2-p-alkylphenyl-5-alkyloxypyrimicin, 4-alkyloxy-4'-biphenylcarboxylic acid-p'-(alkyloxycarbonyl)phenyl ester, 4-alkyloxy-4'-biphenylcarboxylic acid mono-alkyl ester, etc.] and/or ferroelectric liquid crystal [optically active 4-alkyloxy-4'-biphenylcarboxylic acid-p'- (2-methylbutyloxy acid monoalkyl ester, etc.) phenyl) phenyl ester, optically active 4-n-alkyloxy-4'-biphenylcarboxylic acid-2-methylbutyl ester, optically active p-alkyloxybenzylidene-p'-amino-2-chloroprobyl cinnamate, optically active p-alkyloxybenzylidene-p'-
Amino-2-methylbutylcinnamate etc. and/
or ordinary chiral smectic liquid crystal [optically active 4-
(p-alkyloxybiphenyl-p'-oxycarbonyl)''-4'-(2-methylbutyloxycarbonyl)cyclohexane, optically active p-n-alkyloxybenzylidene-p'-(2-methylbutyloxycarbonyl) aniline, etc.], and may also contain chiral compounds and/or dichroic dyes that do not exhibit liquid crystallinity, such as anthraquinone dyes and azo dyes.

A liquid crystal composition exhibiting ferroelectricity causes an optical switching phenomenon when a voltage is applied, and a display element with a fast response can be produced using this phenomenon [for example, Japanese Patent Application Laid-Open Nos. 56-107216 and 1987-118744] , N.A. Clark, S.T. Lagerwal; Applied Ph.
ysics Letter) Egg, 899 (1980)
Such〕.

The liquid crystal composition in the present invention has a cell spacing of 0.5 to 10 μm.
m1 It can be used as an optical switching element (display element) by vacuum-sealing the cell into a liquid crystal cell preferably having a diameter of 0.5 to 3 μm and installing polarizers on both sides.

The above liquid crystal cell has a transparent electrode and an alignment treatment on the surface.
It can be produced by bonding two glass substrates with a spacer in between.

Examples of the spacer include alumina beads, glass fiber, and polyimide film. As the orientation treatment method, ordinary orientation treatment such as polyimide film, rubbing treatment, SiO oblique evaporation, etc. can be applied.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Production of compound No. 2 in Table 1 22.0 g of 0-fluoro-p-iodophenol was dissolved in 80 g of dime-33-tylsulfoxide, and aqueous sodium hydroxide solution (7.4 g/ 30 ml) and 19.6 g of 1-promohebutane were added, and the mixture was stirred at room temperature for 4 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off hexane, 24.0 g of oily p-n-heptyloxy-m-fluoroiodobenzene was obtained.

20 1 ether solution of Gutgnard's reagent prepared from 3.2 g p-n-heptyloxy-m-fluoroiodobenzene and magnesium and 20 1 1 dry tetrahydrofuran solution of 1.5 g 2,5-dibromopyridine. were reacted for 5 hours at room temperature under a nitrogen atmosphere using 51 rng of dichlorobisdiphenylphosphinbutane palladium as a catalyst. The reaction was stopped with water, the reaction mixture was extracted with ether, washed successively with IN hydrochloric acid and water, and the ether was distilled off. The obtained solid was recrystallized from methanol to obtain 4 g of the following compound (a) L.

F Br-Q-d-OC7H+ 5 (a) 1.4 g of the compound (a) obtained in
Using 10 mg of iodized steel (I) and 60 mg of triphenylphosphine, the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with hexane. The hexane layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. By recrystallizing the obtained solid twice from ethanol, 1.1 g of the compound No. 2 in Table 1, which is a compound of the present invention, was obtained. The structure of the compound can be determined by NMR (Nuclear Magnetic Synthesis Spec 1)
- Confirmed by MS (mass spectrometry), IR (infrared absorption spectrum analysis), and elemental analysis. IR spectrum, H-NMR spectrum and F-N of the above compound
The MR spectra are shown in FIGS. 1, 2 and 3, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 7
8.99 C: 79.00I1: 8.61
H: 8.55F: 4.81F:
4.80 N: 3.54 N: 3.60 Example-2 No. in Table-1. Preparation of compound 3 ■ 22.0 g of 0-fluoro-p-iodophenol was dissolved in 80 g of dimethyl sulfoxide, and aqueous sodium hydroxide solution (7.4 g/30 ml) and 21.2 g of 1-bromooctane were added thereto, and the mixture was heated to room temperature. The mixture was stirred for 4 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off the hexane, 25.0 g of oily p-n-octyloxy-m-fluoroiodobenzene was obtained.

■ 3.3 g of p-n-octyloxy-m-fluoroiodobenzene, 20 μl of an ether solution of Grignard reagent prepared from magnesium, and 20 μl of a dry tetrahydrofuran solution of 1.5 g of 2,5-dibromoviridine. Using 57 mg of dichlorobisdiphenylphosphinobutane palladium as a catalyst, the reaction was carried out at room temperature under a nitrogen atmosphere for 5 hours. The reaction was stopped with water, the reaction mixture was extracted with ether, washed successively with IN hydrochloric acid and water, and the ether was distilled off.

By recrystallizing the obtained solid from methanol,
1.5 g of the following compound (b) was obtained.

F Br-Q-d-OC8H+ 7 (b) 1.5 g of compound (b) obtained in ■■ and 550 mg of 1-octyne
In 50 ml of triethylamine, 40 mg of dichlorobistriphenylphosphine palladium and m iodide were added to the catalyst.
(I) 10 mg and triphenylphosphine 6
Using 0 mg, the mixture was heated under reflux under a nitrogen atmosphere for 5 hours.

After cooling, triethylamine was distilled off and extracted with hexane. The hexane layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. The obtained solid was recrystallized twice from ethanol to obtain 1.2 g of the compound of the present invention, No. 3 in Table 1. The IR spectrum, H-NMR spectrum and F--37= NMR spectrum of the above compound are shown in Figures 4, 5 and 6, respectively.
As shown in the figure.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 79.22 C: 79.16H: 8.8
0 +1: 8.85F: 4.65
F: 4.55N: 3.42N: 3.
50 Example-3 No. 3 in Table-1. Preparation of compound No. 8 ■Example-2 Compound (b) obtained in ■1. 5g and 1
620 mg of monononine in 50 mI of triethylamine;
Using 40 mg of dichlorobistriphenylphosphine palladium, 10 mg of steel (I) iodide, and 60 mg of triphenylphosphine as catalysts, the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with hexane. The hexane layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. By recrystallizing the obtained solid from ethanol 2-38 times, Table 1, which is a compound of the present invention, was obtained.
1.2 g of a compound with medium No. 8 was obtained. I of the above compound
R spectrum, H-NMR spectrum and F-NMR
The spectra are shown in FIGS. 7, 8 and 9, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 7
9.38C: 79.16H: 9.04
H: 9.15F: 4.49
F: 4.55N: 3.31 N: 3.3
0 Example-4 No. 0 in Table-1. 3 Production of compound 6 ■ 25.0 g of p-iodophenol and 200 ml of dimethyl sulfoxide
and add sodium hydroxide aqueous solution (8.4g/
30 ml) and 19.3 g of 1-bromohebutane were added, and the mixture was stirred at room temperature for 4 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off hexane, oily p-n-heptyloxyiodobenzene 29.0
I got g.

■ 6.0 g of p-n-heptyloxyiodobenzene and 50 ml of an ether solution of Gutgnard's reagent prepared from magnesium, and 50 n1 liter of a dry tetrahydrofuran solution of 3.0 g of 2,5-dibromopyridine were added to the catalyst in dichloromethane. bisdiphenylphosphinobutane palladium 11
Using 5 mg, the reaction was carried out at room temperature under nitrogen atmosphere for 5 hours. The reaction was quenched with water and the reaction mixture was extracted with ether, IN
After sequentially washing with hydrochloric acid and water, the ether was distilled off. The obtained solid was recrystallized from methanol to obtain 2.0 g of the following compound (c).

Br-Q-0-OC7H,s (c) 1.3 g of compound (c) obtained in ■■ and 540 m of 1-octyne
g in 50 x 1 triethylamine, 40 mg of dichlorobistriphenylphosphine palladium, 10 mg of copper(I) iodide and 60+n of triphenylphosphine as a catalyst.
The mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with hexane.

The hexane layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. The obtained solid was recrystallized twice from ethanol to obtain 0.9 g of the compound of the present invention, No. 36 in Table 1.

The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in FIG. 10 and FIG. 11, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 8
2.76 C: 82.7011: 9.28
H: 9.38N: 3.71N:
3.60 Example-5 No. 5 in Table-1 Preparation of compound 86 ■ 5.0 g of 2-bromo-5-nitropyridine and 3.1 g of 1-nonine in 50 ml of triethylamine, and 204 mg of dichlorobistriphenylphosphine palladium as a catalyst.
Using 51 mg of copper (I) and copper iodide, the reaction was carried out overnight at room temperature under a nitrogen atmosphere. After the reaction was completed, triethylamine was distilled off and extracted with hexane. The hexane layer 41 was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. The obtained solid was recrystallized from methanol to obtain 3.0 g of the following compound (d).

nc7H1 5-C≡C-0-NO2 (d)■
Add 3.0 g of the compound (cl) obtained in (2) to 25 ml of ethanol.
Dissolve in 0ml and add 5% palladium on carbon to this.
5 g was added and hydrogenation was carried out at room temperature under a hydrogen atmosphere at normal pressure. After confirming that no hydrogen was absorbed, the catalyst was removed by filtration, and ethanol was distilled off to obtain 2.5 g of oily 2-n-nonyl-5-aminopyridine.

■2-n into 100+nlO of water containing 11g of 36χ hydrochloric acid
2.5 g of -nonyl-5-aminopyridine was added and the mixture was cooled to 5°C or lower. Add to this aqueous sodium nitrite solution (0.7
2g/5ml) was added dropwise at 5°C or lower. After stirring for another hour after the dropwise addition, potassium iodide aqueous solution (8.6 g
/10 ml) was added, the temperature was slowly returned to room temperature, and the mixture was stirred until no nitrogen was generated. After the reaction is complete, add sodium hydroxide to the solution to make it alkaline and extract with hexane-4
2- I did. The hexane layer is mixed with water, sodium bisulfite aqueous solution,
After successively washing with water, the product was purified by silica gel column chromatography to obtain 2.5 g of oily 2-n-nonyl-5-iodopyridine.

■2.0 g of p-n-octyloxy-m-fluoroiodobenzene obtained in Example-2■ and 30 ml of an ether solution of Grignard reagent prepared from magnesium;
- 2.5 g of n-nonyl-5-iodopyridine dried
- 50 ml of a hydrofuran solution was heated under reflux for 8 hours under a nitrogen atmosphere using 45 mg of dichlorobisdiphenylphosphinobutane palladium as a catalyst. After cooling, the reaction was stopped with water, the reaction mixture was extracted with ether, washed successively with IN hydrochloric acid and water, and the ether was distilled off. The obtained solid was purified by silica gel force column chromatography and then recrystallized twice from methanol to obtain No. 1 in Table 1, which is a compound of the present invention. 0.7 g of compound No. 86 was obtained. The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in FIGS. 12, 13 and 14, respectively.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 78.69 C: 78.60H: 9.8
4H: 9.90N: 3.28
N: 3.30F: 4.45 F: 4.4
4 Example-6 Production of compound No. 114 in Table 1 ■ 15.0 g of 0-fluoro-p-iodophenol was dissolved in 120 ml of dimethyl sulfoxide, and aqueous sodium hydroxide solution (3.0 g/10 ml) and 1-
10.4 g of promohexane was added and stirred at room temperature for 4 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off hexane, 16.7 g of oily p-n-hexyloxy-m-fluoroiodobenzene was obtained.

14.0 g of p-n-hexyloxy-m-fluoroiodobenzene obtained in ■■ and 3-methyl-1-butyne-3-
The reaction mixture was reacted in 80ml of triethylamine using 272mg of dichlorobistriphenylphosphine palladium and 68mg of copper(I) iodide as catalysts under a nitrogen atmosphere at room temperature overnight. After the reaction was completed, triethylamine was distilled off and extracted with hexane. After sequentially washing the hexane layer with IN hydrochloric acid and water, 12.5 g of the following compound (e) was obtained by distilling off the hexane.

F n-C6}1.30-δ-(,'C-C(CH3)2-
12.5 g of compound (e) obtained in OH (e) ■■ was dissolved in 400 ml of dry toluene, 5.4 g of powdered sodium hydroxide was added thereto, and the mixture was heated under reflux for 1 hour. After cooling and washing with water, toluene was distilled off. After the obtained black oil was extracted with methanol, the methanol was distilled off to obtain 7.55 g of oily p-n-hexyloxy-m-fluorophenyl acetylene.

120 ml of an ether solution of Grignard reagent prepared from 15.0 g of p-n-hexyloxy-m-fluoroyodobenzene obtained in ■■ and magnesium, and a dry tetrahydrofuran solution of 13.2 g of 2,5-dipromopyridine 1 Using 338 mg of dichlorobisdiphenylphosphinobutane palladium as a catalyst, the mixture was reacted at room temperature under a nitrogen atmosphere for 5 hours. Stop the reaction with water, −
45- The reaction mixture was extracted with ether, washed successively with 1N hydrochloric acid and water, and then the ether was distilled off. By recrystallizing the obtained solid from methanol, 10.0 g of the following compound (f) was obtained.
I got it.

F Br-Q-d-OCeH+ 3 (f) 2.0 g of compound (f) obtained in ■■ and 1.6 g of p-n-hexyloxy-m-fluorophenyl acetylene obtained in ■ in 50 ml of triethylamine. Catalyst: 122 mg of dichlorobistriphenylphosphine palladium, copper(I) iodide
Using 31 mg and 160 mg of triphenylphosphine, the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with toluene. The toluene layer was washed successively with IN hydrochloric acid and water, and then purified using silica gel column chroma 1 graphie.

The obtained solid was recrystallized twice with ethanol to obtain Compound 2, No. 114 in Table 1, which is a compound of the present invention.
．． Obtained 0g. IR spectrum of the above compound, H-NM
The R spectrum and F-NMR spectrum are shown in Figures 15, 16, and 17-46, respectively.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 75.76 C: 75.70H: 7.1
3H: 7.23F: 7.74
F: 7.82N: 2.85 N: 2.8
3 Example-7 Production of compound No. 108 in Table 1 ■ 25.0 g of p-iodophenol was dissolved in 250 ml of dimethyl sulfoxide, and aqueous sodium hydroxide solution (5.0 g/20 ml) and n-hexyl bromide 17 .8 g was added and stirred at room temperature for 3 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off the hexane, 29.5 g of oily p-n-hexyloxyodobenzene was obtained.

■p-n-hexyloxyiodobenzene 29.5g
and 12.4 g of 3-methyl-1-butyn-3-ol were reacted in 150 mI of triethylamine using 300 mg of dichlorobistriphenylphosphine palladium and 75 mg of copper(I) iodide as catalysts under a nitrogen atmosphere at room temperature overnight. Ta. After the reaction was completed, triethylamine was distilled off and extracted with hexane. The hexane layer was diluted with IN hydrochloric acid and water for 11 hours.
After the k-th washing, hexane was distilled off to obtain 23.2 g of the following solid compound (g).

n-C6H130-()-C≡C-C(CH3)2-O
23.2 g of the compound (g) obtained in H(g) 7 g was added and heated under reflux for 1 hour. After cooling,
After washing with water, toluene was removed. After the obtained black oil was extracted with methanol, the methanol was distilled off to obtain 12.8 g of oily p-n-hexyloxy-phenylacetylene.

■Example-6 2.0 g of compound (f) obtained in ■■ and 1.5 g of p-n-hexyloxifu-engineered nylacetylene obtained in ■
In 50 ml of triethylamine, the catalyst was mixed with 122 mg of dichlorobistriphenylphosphine palladium, 31 mg of copper(I) iodide, and 160 mg of triphenylphosphine.
The mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with toluene. The toluene layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography.

The obtained solid was recrystallized twice with ethanol to obtain Compound 1, No. 108 in Table 1, which is a compound of the present invention.
．． 7g was obtained. IR spectrum of the above compound, H-N
The MR spectrum and F-NMR spectrum are shown in FIGS. 18, 19 and 20, respectively.

Elemental analysis values: Theoretical value (%) C: 78.65 H: 7.61 F: 4.02 N: 2.96 Actual value (%) C: 78.71 H: 7.60 F: 4.00 N : 2.93 Example-8 Production of compound No. 117 in Table-1 ■ 30.0 g of p-n-hexyl-iodobenzene and 3-
10.5 g of methyl-1-butyn-3-ol was added to 200 ml of triethylamine-49, and 330 mg of dichlorobistriphenylphosphine palladium and copper (I) iodide were added as catalysts.
Using 80 mg, the reaction was carried out at room temperature under a nitrogen atmosphere for one day. After the reaction was completed, triethylamine was distilled off and extracted with hexane. After sequentially washing the hexane layer with IN hydrochloric acid and water, the following oily compound (h) 25 was obtained by distilling off the hexane.
．． 4g was obtained.

n-C6H13-0-CEC-C(Cll3)2-01
1 (h) 25.4 g of compound (h) obtained in ■■ was dissolved in 800 ml of dry toluene, 12.5 g of powdered sodium hydroxide was added thereto, and the mixture was heated under reflux for 1 hour. After cooling, toluene was removed after washing with water. After extracting the obtained black oil with methanol, the methanol is distilled off to obtain oily p-n-hexylphenyl acetylene 15. 1g was obtained.

■Example-6 2.0 g of the compound (f) obtained in ■ and 1.4 g of p-n-hexylphenylacetylene obtained in , iodized steel (I) 3
Using 1 mg and 160 mg of triphenylphosphine, the mixture was heated under reflux for 5 hours under a -50 nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with toluene. Toluene layer I
After sequentially washing with N-hydrochloric acid and water, the product was purified by silica gel column chromatography. The obtained solid was recrystallized twice with ethanol to obtain N in Table 1, which is a compound of the present invention.
1.6 g of compound No.o,117 was obtained. IR of the above compound
The spectrum, H-NMR spectrum and F-NMR spectrum are shown in FIGS. 21, 22 and 23, respectively.

Elemental analysis values: Actual value (%) C: 83.20 H: 8.07 F: 4.20 N: 3.20 Theoretical value (%) C: 83.22 H: 8.05 F: 4.25 N : 3.13 Example-9 Production of compound No. 1 1 1 in Table-1 ■ 25.0 g of p-iodophenol was mixed with 200 m of dimethyl sulfoxide.
1, and add sodium hydroxide aqueous solution (8.4 g
/30ml) and 17.8g of 1-bromohexane were added, and the mixture was stirred at room temperature for 4 days. The reaction mixture was extracted with hexane and washed with water three times. By distilling off hexane,
Oily p-n-hexyloxyiodobenzene31.
Obtained 0g.

■ p-n-hexyloxyiodobenzene 15.0g
120 ml of a solution of Grignard reagent prepared from magnesium and 2,5-dibromoviridine 14.
0g of dry tetrahydrofuran solution was reacted with 120ml of a solution of 0g of dry tetrahydrofuran for 5 hours at room temperature under a nitrogen atmosphere using 357mg of dichlorobisdiphenylphosphinobutane palladium as a catalyst. The reaction was stopped with water, the reaction mixture was extracted with ether, washed successively with IN hydrochloric acid and water, and then the ether was distilled off. The obtained solid was recrystallized from methanol to obtain 8.9 g of the following compound (i).

Br-Q-0-OCeH+a (i) 1.9 g of compound (i) obtained in ■■ and p-n obtained in Example-60
-hexyloxy-m-fluorophenyl acetylene 1
．． 6 g in 50 ml of triethylamine, 22 mg of dichlorobistriphenylphosphine palladium 1 as a catalyst,
Using 31 mg of copper(I) iodide and 60 mg of triphenylphosphine 1, the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, triethylamine was distilled off and extracted with toluene. The toluene layer was washed successively with IN hydrochloric acid and water, and then purified by silica gel column chromatography. The obtained solid was recrystallized twice with ethanol to obtain compound 1.5 of No. 1 1 1 in Table 1, which is a compound of the present invention.
I got g. The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound were measured in the 24th column, respectively.
25 and 26.

Elemental analysis values: Theoretical value (%) C: 78.65 H: 7.61 F: 4.02 N: 2.96 Actual value (%) C: 78.55 H: 7.53 F: 4.00 N : 3.06 -53- Example-10 No. in Table-1. Production Example-9 of compound 1 3 3
500 mg of the compound No. 111 in Table 1 obtained above was suspended in 20 x 1 of ethanol, 100 mg of 5% palladium carbon was added thereto, and hydrogenation was performed at room temperature under a hydrogen atmosphere at normal pressure. After confirming that no hydrogen was absorbed, the catalyst was removed by filtration and the ethanol was distilled off. The obtained solid was purified by silica gel column chromatography and then recrystallized twice from ethanol to obtain 350 mg of the compound of the present invention, No. 133 in Table 1.

The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in Figures 27 and 28, respectively.
and FIG. 29.

Elemental analysis values: Theoretical value (%) C: 77.99 N: 8.39 F: 3.98 N: 2.94 Actual value (%) C: 77.70 H: 8.45 F: 4.01 N : 3.01 -54 Example-1, Example-2, Example-3, Example-4, Example-5, Example-6, Example-7, Example-8, Example- Table 2 shows the phase transition temperatures of the compounds obtained in Example 9 and Example 10.

Table-2 (1) Table-2 (2) Each symbol in Table 2 is as follows.

Cry crystalline phase S, unidentified smectic phase Sc Smectic C phase S, smectic A phase N Nematic phase Iso Isotropic liquid phase One phase does not exist Moreover, these smectic liquid crystals have the following remarkable characteristics.

(1) Negative dielectric anisotropy is required for liquid crystal compositions, and the smectic C liquid crystal of the present invention contains electron-withdrawing halogen atoms bonded and/or nitrogen atoms in the short axis direction of the molecule. Therefore, it has a negative dielectric anisotropy, and is very useful as a component for making the dielectric anisotropy of a liquid crystal composition negative.

-57- (2) In particular, the smectic C liquid crystal of the present invention in which fluorine atoms are bonded has no other smectic phase on the lower temperature side than the smectic C phase, so mixing can widen the temperature range of the smectic C phase, making it very useful. be.

(3) Among the smectic liquid crystals of the present invention, those having a Cry-So phase series can lower the lower limit temperature of the smectic C phase by mixing, and are extremely useful as components for expanding the temperature range of the smectic C phase. It is useful for

(4) Low viscosity because there is no ester bond in the molecule.

(5) Excellent compatibility with other smectic C liquid crystals.

(6) Since the molecules are rigid, the orientation is very good.

(7) Good stability against light, heat, and moisture.

(8) Since the smectic liquid crystal of the present invention has an acetylene bond, it has a large birefringence, and therefore, by adding it not only to a smectic C liquid crystal composition but also to a nematic liquid crystal composition, it can be added to a liquid crystal display cell-58-. The response speed can be increased by reducing the thickness.

Since the liquid crystal compound of the present invention exhibits the above effects, it is a very useful substance in developing a practical ferroelectric smectic liquid crystal composition.

[Brief explanation of drawings]

Figures 1, 2, and 3 show the IR, H-NMR, and F-NMR spectra of the compound obtained in Example 1, respectively, and Figures 4, 5, and 6 show the results of the example. Figures 7, 8 and 9 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example-3, respectively. -N
Figures 10 and 11 show the IR and H-NMR spectra of the compound obtained in Example-4, respectively, and Figures 12, 13, and 14 show the IR and H-NMR spectra of the compound obtained in Example-5, respectively. IR, H-NMR and F-
Figures 15, 16, and 17 show the NMR spectra of the compound obtained in Example-6, respectively.
The R and F-NMR spectra are shown in Figures 18, 19, and 20, respectively, of the compound obtained in Example-7.
The R,H-NMR and F-NMR spectra were
Figures 22 and 23 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example-8, respectively, and Figures 24, 25 and 26 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example-9, respectively. IR, H-NMR and F-N of the compound obtained in
Figures 27, 28, and 29 show the MR spectra of the compound obtained in Example-10, IR and H-NM, respectively.
R and F-NMR spectra are shown.

Claims (1)

[Claims] 1. General formula R-X^1-(-A^1-X^2-)n-A^2-A^
3-X^3-R' (1) [In the formula, R and R' have 1 to 1 carbon atoms
18 alkyl group, X^1 is a direct bond, -O-, -S
- or -C≡C-, A^1, A^3 are 1,4 which may be substituted with 1 to 4 fluorine atoms or chlorine atoms
-phenylene group, n is 0 or 1, X^2 is -C≡
C- or -CH_2CH_2-, A^2 is ▲ formula,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X^3 is a direct bond, -O- or -S
- (However, if n is 0 and A^2 is ▲ there is a mathematical formula, chemical formula, table, etc. ▼, then X^1 is -C≡C-)]
A pyridine-based liquid crystal compound represented by