JPH03218364A - Pyridazine-based liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R and R' are each 1-18C alkyl; X<1> and X<2> are each single bond, O, S or CidenticalC; Y is CH2CH2 or CidenticalC; A is (F- and/or Cl-substituted) 1,4-phenylene, 4,4'-biphenylene or 2,6-naphthylene]. USE:A liquid crystal display element material. Giving smectic C crystal, negative in dielectric constant anisotropy, large in tilt angle, highly compatible with other smectic C liquid crystals, capable of widening effective temperature range by mixing, low in viscosity, and highly stable to light, heat and moisture. PREPARATION:A reaction is made between a compound of formula II (Y' is Br or I) and a compound of formula HCidenticalC-A-X2-R' in triethylamine under an inert gas atmosphere using a 0- or divalent palladium catalyst to obtain the objective compound of the formula I (where Y is CidenticalC).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel pyridazine-based liquid crystal compound useful for display devices.

-1- [Prior art] 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 (NA Clark et al.;
Applied Phys. let. , 36, 8
99 (1980)). This method utilizes a chiral smectic phase such as a chiral smectic C phase that exhibits ferroelectricity. It is known that the chiral Sc phase is not the only phase that exhibits ferroelectricity, but also chiral smectic F, G, -2-H, ■, and other phases exhibit ferroelectricity.

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

In addition to ferroelectric liquid crystal compositions consisting only of ferroelectric liquid crystal compounds, JP-A No. 60-36003 discloses compounds exhibiting non-chiral smectic C, F, G, H, 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, -3-327 (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 it exhibits a ferroelectric liquid crystal phase.

Various compounds such as smectic C which exhibit a non-irradial smectic liquid crystal phase can be used as these basic substances, 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.

[Problems to be solved by the invention] However, it is unclear whether chiral smectic C liquid crystal 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-4-crystal displays that utilize ferroelectricity have not yet been technically perfected. Therefore, it is currently necessary to test various new materials for Smectic C liquid crystal compositions.

[Means for Solving the Problems] The present inventors have conducted intensive studies on new liquid crystal compounds suitable for use in the above-mentioned applications and are useful in Smectic C liquid crystal compositions, and as a result, have arrived at the present invention. did. That is, the present invention provides general formula R-X, -Q-Y-A-X2-R'
(1) [In the formula, R and R' are alkyl groups having 1 to 18 carbon atoms, x, X2 are single bonds (direct bonds),
-0--S1 or 1C301, Y is -CH2C
H2- or -C=C-, and A is a 1,4-phenylene group, 4,4'-biphenylene group, which may be substituted with a fluorine atom or a chlorine atom (one or (two CH groups may be replaced by N) or a 2,6-naphthylene group].

-5 In the general formula (1), the alkyl group having 1 to 18 carbon atoms for R and R' includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. group, n-heptyl group, n-octyl group, n-nonyl 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 3 to 14 carbon atoms.

A is preferably 1, which may be substituted with a fluorine atom,
4-phenylene group, 4.4'-biphenylene group or 2
, 6-naphthylene group.

Groups in which one or two CH groups present in the 1,4-phenylene group and 4,4'-biphenylene group are replaced with N include -0-, -Q-, -G-, -D −、−
Examples include Q-, -0-, -0-0-, -Q-0-, and the like.

As a specific example of the compound represented by the general formula (1), Table-
Examples include compounds having groups as shown in Tables 1 to 2.

16- (1) When Y is -C3C- 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) -13- Table-1 (8) -141 Table-1 (9) Table-1 (10) Table-1 (11) -17- Table-1 (12) -18- Table-1 (13) Table-1 (14) Table-1 (15) -21- Table-1 (16) -22- (2) When Y is -CH2CH2- Table-2 (1) In Table-1, each symbol represents the following group.

BUT' nC,,t{g- PEN nC51{H- HEX nC6H13- HEP nC7H1s- OCT nC6 81? - NON nCg 111 9 - DEC nC, 3H2, - tJND nC1 1 H23 - DOD nC, 2H25-TED nC, 4H29 - NAP}ITHIL; 2, 6-naphthylene group; Ac representing a single bond; -CmiC- The compound included in the general formula (1) can be synthesized, for example, through the following steps. (In the following formula, R, '(Y'; Br 1) (2) That is, the compound of general formula (2) and the compound of general formula (3) are reacted in triethylamine under an inert gas atmosphere using a zero- or divalent palladium catalyst. By this, a compound of general formula (1a), which is a compound of the present invention, can be obtained.

Or R-X, -Q-Y' (2) -25- (4) R-X, -Q-CmiCH (5) That is, the compound of general formula (2) and 3-methyl-1-butyn-3-ol and triethylamine in an inert -gas atmosphere using a zero- or divalent palladium catalyst to obtain a compound of general formula (4), and then reacted with powdered sodium hydroxide in anhydrous toluene. General formula (
Compound 5) can be obtained. By reacting the compound of general formula (5) and the compound of general formula (6) in triethylamine under an inert gas atmosphere using a zero- or divalent palladium catalyst, the compound of the general formula (1a), which is a compound of the present invention, is obtained. ) can be obtained.

Moreover, the compounds of general formulas (2) and (5) can be synthesized, for example, through the following steps.

■When X is a single bond, V-Q-Y (V; Cl, Br) (
7)-27-R-Q-Y-281(2a) That is, the compound of general formula (7) and the compound of general formula (8) are mixed in triethylamine under an inert gas atmosphere as a zero-valent or divalent palladium catalyst. A compound of general formula (9) can be obtained by reaction using. General formula (9
) is hydrogenated using platinum dioxide in a hydrogen atmosphere to obtain the compound of the general formula (
Compound 2a) can be obtained. The compound of general formula (2a) is reacted with 3-methyl-1-butyn-3-ol in triethylamine in an inert gas atmosphere using a zero- or divalent palladium catalyst to form a compound of general formula (10). Thereafter, the compound of general formula (5a), which is the raw material for the compound of the present invention, can be obtained by reacting powdered sodium hydroxide in anhydrous toluene.

■In the case of X, ○1, Y-Q-V (Y; Cl, Br) (
7) -29- RO-Q-Y CI{3 RO-Q-CECH -30- (2b) (5b) A compound of general formula (2b), which is a raw material for the compound of the present invention, can be obtained. The compound of general formula (2b) is reacted with 3-methyl-1-butyn-3-ol in triethylamine in an inert gas atmosphere using a zero- or divalent palladium catalyst to form a compound of general formula (11). After that, by reacting powdered sodium hydroxide in anhydrous toluene, the general formula (
Compound 5b) can be obtained.

■When X1 is -C=C- Y'-/:)-Y' (7) CH3 In other words, the compound of general formula (7) and the 1-alkyne represented by general formula (12) are inactivated in triethylamine. The general formula (
Compound 2C) can be obtained. The compound of general formula (2C) is reacted with 3-methyl-1-butyn-3-ol in triethylamine in an inert gas atmosphere using a zero- or divalent palladium catalyst to form a compound of general formula (13). After that, the compound of general formula (5C), which is a raw material for the compound of the present invention, can be obtained by reacting powdered sodium hydroxide in anhydrous toluene.

Moreover, the compounds of general formulas (3) and (6) can be synthesized, for example, through the following steps.

(F) ■X2 is 10-, A is -O-, -0-0- or 2,6
In the case of naphthylene group (Y'; Br or l) Y'-A-OM (M; Li, Na or
K) (14)-33- 1 C■3 That is, by alkylating the compound of general formula (14) with an alkylating agent (for example, an alkyl halide), the compound of general formula (6a), which is a raw material for the compound of the present invention, can be obtained. Compounds can be obtained. The compound of general formula (6a) is reacted with 3-methyl-1-butyn-3-ol in triethylamine in an inert gas atmosphere using a -34-0- or divalent palladium catalyst to obtain general formula (15). The compound of general formula (3a), which is a raw material for the compound of the present invention, can be obtained by reacting powdered sodium hydroxide in anhydrous toluene.

F ■If X2 is -O- and A is -od-F Y'-d-OH (Y'; Br or l)
(16) v'-o-o-oc-o (19) v'-0-d-oM ↓ F Y '-0-0-OR' H0-C-C E C-0-0-OR 'CH3 ↓ -37- (21) 0 (6b) (22) HC:C-0-0-OR' (3b) That is, the compound of general formula (17) obtained by esterifying the compound of general formula (16) with penzoyl chloride A compound of general formula (18) can be obtained by reacting the compound and phenylboric acid in the presence of a palladium catalyst. The compound of general formula (18) is halogenated with a halogenating agent (for example, periodic acid + iodine), and then hydrolyzed with an alkali (for example, sodium hydroxide) to isolate and purify the compound of general formula (20). can be obtained. The compound of general formula (6b), which is a raw material for the compound of the present invention, is obtained by reacting the compound of general formula (20) with an alkali metal hydroxide and then alkylating it with an alkylating agent (for example, an alkyl halide). can be obtained. The compound of general formula (6b) and 3-methyl-1-butyn-3-ol are reacted in triethylamine under an inert gas atmosphere using a zero- or divalent palladium catalyst to obtain the general formula -38- (22). The compound of general formula (3b), which is a raw material for the compound of the present invention, can be obtained by reacting with powdered sodium hydroxide in anhydrous toluene.

■When X2 is a single bond and A is 101, R'-0-NH2 (23) R'-0-Y' (6c) That is, the compound of general formula (23). After diazotization, the alkali metal halogen By reacting with a compound, a compound of general formula (6c), which is a raw material for the compound of the present invention, can be obtained. The compound of general formula (24) is obtained by reacting the compound of general formula (6c) with 3-methyl-1-butyn-3-ol in triethylamine under an inert gas atmosphere using a zero- or divalent palladium catalyst. can be obtained. By reacting the compound of general formula (24) with powdered sodium hydroxide in anhydrous toluene, the compound of general formula (3c), which is the origin of the compound of the present invention, can be obtained.

(2) When Y is -CH2CH2-R-X, -Q-CEC-A-X2-R' (1a) R-X, -Q-Cll2CH2-A-X2-R'
(lb) That is, the compound of general formula (1b), which is the compound of the present invention, can be obtained by hydrogenating the compound of general formula (1a) using palladium carbon in a hydrogen atmosphere.

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 having no optically active sites [2-p-alkyloxyphenyl-5-alkylpyrimidine, 21p-alkylphenyl-5-alkyloxypyrimidine, 2-p-alkylphenyl-5-alkyloxypyrimidine, -alkanoyloxyphenyl-5-alkylpyrimidine, 2-p-alkyloxylponylphenyl-5-alkylpyrimidine, 2-p-alkylphenyl-5-p-alkyloxyphenylpyrimidine, 2-p-alkyloxy- m-fluorophenyl-5
-Alkylpyrimidine, 2-p-alkyloxyphenyl-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-alkylphenylpyrimicine, p-alkyloxyphenyl-5-
Alkyl bicolinate, 2-p-alkyloxyphenyl-5-alkyloxyvirazine, 2-p-alkylphenyl-5-alkylpyrimicin, 2-p-alkyloxyphenyl-5-alkyloxypyrimicin, 2- p
-alkylphenyl-5-alkyloxybilimicin,
4-alkyloxy-4'-biphenylcarboxylic acid monop
'-(alkyloxycarbonyl)phenyl ester,
4-alkyl-42-yloxy-4'-biphenylcarboxylic acid monoalkyl ester and/or ferroelectric liquid crystal [optically active 4
-alkyloxy-4'-biphenylcarboxylic acid-p'
-(2-methylbutyloxycarbonyl)phenyl ester, optically active 4-n-alkyloxy-4'-biphenylcarboxylic acid-2-methylbutyl ester, optically active p-alkyloxybenzylidene-p'-amino-2-
chloroprovir cinnamate, optically active p-alkyloxybenzylidene-p'-amino-2-methylbutylcinnamate, etc.] and/or ordinary chiral smectic liquid crystals [optically active 4-(p-alkyloxybiphenyl-p'-oxy carbonyl')-4'-(2-
Methylbutyloxycarbonyl)cyclohexane, optically active p-n-alkyloxybenzylidene-p'-(2
-Methylbutyloxycarbonyl)aniline and the like. It 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. CI ark, S.T. Lagerwal I; Applied Physics Letters (Appliecl)
Physics Lttetter) Father, 899 (1
980) etc.].

The liquid crystal composition in the present invention has a cell spacing of 0.5 to 10 μm.
It can be used as an optical switching element (display element) by vacuum-sealing it in a liquid crystal cell with a diameter of 0.5 to 3 m, preferably 0.5 to 3 m, 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. 21 in Table 1 ■ 7.0 g of 3,6-dichloropyridazine and 1-decyne 3
．． 2g of bistriphenylphosphinepalladium dichloride as a catalyst in 70ml of triethylamine.
The mixture was refluxed for 1 hour under a nitrogen atmosphere using 45 mg of copper (I) and 45 mg of copper (I) iodide. After the reaction was completed, triethylamine was removed and the mixture was extracted with hexane. The hexane layer was washed with hydrochloric acid and water, and then subjected to silica gel ram treatment to obtain 3.0 g of the following compound (a) in the form of an oil.

nC8H,7-CmiC-Q-CI
(a)■1.4L of water containing 210g of sodium hydrogen carbonate
Add 187g of medium heorthofluorophenol to 10
Cooled below ℃. Iodine 423 finely crushed into this
g was added in 5 portions. After confirming that the color of iodine had disappeared, the mixture was extracted with toluene. Water-45 toluene layer
The toluene was removed after first washing, washing with sodium bisulfite water, and then washing with water. Vacuum distillation (bpl24~
The reddish-purple liquid obtained at 145° C./18 mmt {g) was recrystallized from hexane to obtain 120 g of white crystal 0-fluoro-p-iodophenol.

15.0 g of the above 0-fluoro-p-iodophenol dissolved in 120 ml of dimethyl sulfoxide was added to a solution of sodium hydroxide (3.0 g of sodium hydroxide,
10 ml of water was added and stirred until a homogeneous solution was obtained.

Next, 10.4 g of n-hexyl bromide was added and stirred at room temperature for 3 days. The reaction solution was poured into ice water and extracted three times with hexane. After washing the hexane layer with water,
By removing hexane, 16.7 g of oily p-n-hexyloxy-m-fluoroiodobenzene was obtained.

■14.0 g of p-n-hexyloxy-m-fluoroiodobenzene and 3-methyl-1-butyn-3-ol in 80 ml of triethylamine, using 272 mg of bistriphenylphosphine palladium dichloride and 68+ ng of copper (I) iodide as catalysts. The mixture was reacted day and night at room temperature under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed and the mixture was extracted with hexane. The hexane layer was washed with IN hydrochloric acid and water, and then the hexane was removed to obtain 12.5 g of the following compound (b).

CH3 ■■ 12.5g of compound (b) obtained in dry toluene 40g
5.4 g of powdered sodium hydroxide was added to the solution dissolved in 0 ml and heated under reflux for 1 hour. After cooling, toluene was removed after washing with water. After extracting the obtained black oil with methanol, 7.55 g of oily p-n-hexyloxy-m-fluorophenyl acetylene was obtained by removing the methanol.

1.6 g of compound (a) obtained in ■■ and 1.4 g of p-n-hexyloxy-m-fluorophenyl acetylene obtained in
g in 30 ml of triethylamine, 40 mg of bistriphenylphosphine palladium dichloride, 10 mg of copper(I) iodide and 60 mg of triphenylphosphine as a catalyst.
The mixture was refluxed for 5 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, and then treated with a silica gel ram, followed by recrystallization twice with methanol to obtain 0.95 g of the compound No. 21 in Table 1, which is a compound of the present invention.

The structure of the compound was confirmed by NMR (nuclear magnetic resonance spectroscopy), MS (mass spectrometry), IR (infrared absorption spectroscopy), and elemental analysis. The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in FIGS. 1, 2 and 3, respectively.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 77.42 C: 77.25H: 8.0
6 H: 8.36 N: 6.45
N: 6.21F: 4.38 F: 4.4
5 Example 2 Manufacture of compound No. 146 in Table 1 ■ Into a solution of 25.0 g of p-iodophenol dissolved in 250 ml of dimethyl sulfoxide, aqueous sodium hydroxide (5.0 g of sodium hydroxide, 20 ml of water)
was added and stirred until a homogeneous solution was obtained. Next, 17.8 g of n-hexyl bromide was added and stirred at room temperature for 3 days. After pouring the reaction solution into ice water, dilute with hexane 3
Extracted twice. After washing the hexane layer with water, 29.5 g of oily p-n-hexyloxyodobenzene was obtained by removing the hexane.

■29.5 g of p-n-hexyloxyodobenzene and 12.4 g of 3-methyl-1-butyn-3-ol in 150 ml of triethylamine, and 300 mg of bistriphenylphosphine palladium dichloride and 75 mg of iodized steel (I) as a catalyst. The reaction was carried out overnight at room temperature under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed and the mixture was extracted with hexane. The hexane layer was washed with IN hydrochloric acid and water, and then the hexane was removed to obtain 23.2 g of the following compound (c) as a solid.

-49-C]13 n-C6}11 30-0-C=C-C-0}1
(c) CH3 23.2 g of compound (c) obtained in ■■ was added to 80 g of dry toluene.
10.7 g of powdered sodium hydroxide was added to the solution dissolved in 0 ml and 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 was removed to obtain 12.8 g of oily p-n-hexyloxyphenylacetylene.

1.0 g of p-n-hexyloxyphenylacetylene obtained in step 2 and 1.2 g of compound (a) obtained in step 1 of Example 1 were added to 30 mI of triethylamine, and 40 mg of bistriphenylphosphine palladium dichloride was added as a catalyst. Copper(I) iodide 10 mg and triphenylphosphine 60
The mixture was refluxed for 5 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then treated with a silica gel ram, and then recrystallized twice with methanol to obtain 0.68 g of the compound of the present invention, No. 146 in Table 1, which has -50- Ta.

The IR spectrum and H-NMR spectrum of the above compound are shown in FIG. 4 and FIG. 5, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 8
0.77C:80.53H:8.65
II: 8.79N: 3.85
N: 4.09 Example 3 Production of compound No. 71 in Table 1 ■ 17.6 g of n-decyl alcohol was added to 400 ml of dry dimethylformamide containing 2.67 g of sodium hydride at 70 to 80° C. until hydrogen was generated rapidly. It dripped at a speed that should not be exceeded. When hydrogen is no longer generated, return the temperature to room temperature and add 25.0 g of 3,6-dichloropyridazine into the solution.
g was added thereto and the mixture was refluxed for 2 hours. After the reaction was completed, the solution was poured into ice water, and the resulting precipitate was filtered and dried. The hexane-capable portion of the obtained solid was subjected to silica gel ram treatment and then recrystallized with methanol to obtain 19.4 g of 3-n-1-decyloxy-6-chloropyridazine.

■3-n-1decyloxy-6-chloropyridazine 1.0
g and 0.8 g of p-n-hexyloxy-m-fluorophenyl acetylene obtained in Example 1 (1) in 30 ml of triethylamine, 40 mg of bistriphenylphosphine palladium dichloride and 10 mg of steel iodide (I) as catalysts.
The mixture was refluxed for 5 hours under a nitrogen atmosphere using 60 mg of triphenylphosphine. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then treated with a silica gel ram, and then recrystallized twice with methanol to obtain 0.65 g of compound No. 71 in Table 1, which is a compound of the present invention. The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in FIGS. 6, 7 and 8, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 7
4. OO C: 74.23H: 8.59
H: 8.43N: 6.17N:
6.06F: 4.19F: 4.3
1 Example 4 Production of compound N096 in Table 1 ■ 1.2 g of 3-n-1decyloxy-6-chloropyridazine obtained in (■) of Example 3 and p-n-hexyloxyphenyl obtained in (■) of Example 2 0.9 g of enyl acetylene in 30 ml of triethylamine, 40 mg of bistriphenylphosphine palladium dichloride as a catalyst, 10 iodized steel (I)
The mixture was refluxed for 5 hours under a nitrogen atmosphere using 60 mg of triphenylphosphine and 60 mg of triphenylphosphine. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then subjected to silica gel ram treatment, and then recrystallized twice with methanol to obtain 0.74 g of compound No. 96 in Table 1, which is a compound of the present invention.
I got it. IR spectrum and H-NMR of the above compound
The spectra are shown in FIGS. 9 and 10, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) -53
- C: 77.07 C: 76.83H: 9
．． 17 Old 9.31 N: 6.42 N: 6.28 Example 5 Production of compound N021 in Table 1 ■ Compound (a) obtained in the same manner as ■ in Example 1 6.8
Dissolve g in 100 ml of ethanol and add 210 g of platinum dioxide.
Itlg was added and hydrogenation was performed under a hydrogen atmosphere at normal pressure. When hydrogen absorption ceased, the catalyst was removed by filtration, and then the ethanol was removed. By recrystallizing twice from hexane, 3.1 g of 3-n-decyl-6-chloropyridazine was obtained as a white solid.

■1.9 g of p-n-hexyloxy-m-fluorophenyl acetylene obtained in the same manner as in Examples 1 to 2 and 2.2 g of 3-n-decyl-6-chloropyridazine obtained in
In 50 ml of triethylamine, 100 mg of bistriphenylphosphine palladium dichloride, 25 mg of copper (I) iodide, and 150 mg of triphenylphosphine were used as catalysts, and the mixture was refluxed for 5 hours under a nitrogen atmosphere.

-54- After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then subjected to silica gel ram treatment, and then recrystallized twice with ethanol to obtain compound No. 1 in Table 1, which is a compound of the present invention.
-2 1.75 g of compound 1 was obtained. IR spectrum, H-NMR spectrum and F-NM of the above compound
The R spectra are shown in Figures 11, 12 and 1, respectively.
Shown in Figure 3.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 76.72 C: 76.56H: 8.9
0H: 9.12N: 6.39
N: 6.24F: 4.34F: 4.2
9 Example 6 Production of compound N046 in Table 1 ■ 3-n-decyl-6 obtained in the same manner as in Example 5 ■
- 1.3 g of chloropyridazine and 1.0 g of p-n-hexyloxyphenylacetylene obtained in the same manner as in Example 2 ① to ① were added in 30 ml of triethylamine, and 56 ml of bistriphenylphosphine palladium dichloride was added as a catalyst.
The mixture was refluxed for 5 hours under a nitrogen atmosphere using 14 mg of copper(I) iodide and 94 mg of triphenylphosphine.

After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then subjected to a silica gel ram treatment, and then recrystallized twice with ethanol to obtain NO46 in Table 1, which is a compound of the present invention.
0.83g of the compound was obtained. The IR spectrum and H-NMR spectrum of the above compound are shown in FIG. 14 and FIG. 15, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 8
0.00 C: 79.83H: 9.52
H: 9.63N: 6.67N:
6.81 Example 7 Production of Compound No. 178 in Table 1 ■ 11.4 g of n-hexyl alcohol is added to 400 ml of dry dimethylformamide containing 2.67 g of sodium hydride at 70 to 80°C without causing significant hydrogen evolution. Dropped at speed. When hydrogen is no longer generated, return to room temperature.
25.0 g of 3,6-dichloroviridazine into the solution.
was added and refluxed for 2 hours. After the reaction was completed, the solution was poured into ice water, and the resulting precipitate was filtered and dried. The hexane-capable portion of the obtained solid was treated with a silica gel ram and then recrystallized with methanol to obtain 13.5 g of 3-n-hexyloxy-6-chloropyridazine.

6.0 g of 3-n-hexyloxy-6-chloropyridazine obtained in ■■ and 3-methyl-1-butyn-3-ol 3
．． 5g of bistriphenylphosphinepalladium dichloride as a catalyst in 80cm of triethylamine 200+n
The mixture was refluxed for 8 hours under a nitrogen atmosphere using 50 mg of copper (I) iodide and 400 mg of triphenylphosphine.

After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, and then the toluene was removed to obtain 6.6 g of the following -57- compound (d).

CH3 nC6H, 30-, Q-C=CCOH
(d) CH3 6.6 g of compound (d) obtained in ■■ was added to 200 g of dry toluene.
1.5 g of powdered sodium hydroxide was added to the solution dissolved in tnl, and the mixture was heated under reflux for 1 hour. After cooling, toluene was removed after washing with water. The obtained black solid was recrystallized from hexane to obtain 2.3 g of 3-n-hexyloxy-6-ethynylpyridazine.

(2) 30.0 g of O-fluoro-p-iodophenol was dissolved in 300 ml of anhydrous toluene, 1611 of pyridine was added, and the mixture was stirred at room temperature. This includes penzoyl chloride 17.6
ml was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was washed successively with water, IN hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and water, and then toluene was distilled off. The obtained solid was recrystallized from methanol to obtain 38.2 g of the following compound (e).

F 1 -()-0CO-() (e)-58- 12.8 g of compound (e) obtained in
ml, 25 ml of 2M aqueous sodium carbonate solution was added, and the mixture was stirred at room temperature. To this, under an inert gas atmosphere, 880 mg of tetrakistriphenylphosphine palladium,
30 ml of an ethanol solution containing 5.0 g of phenylboric acid was added, and the mixture was heated under reflux for 5 hours. After cooling, the reaction was stopped with 3 ml of 30% hydrogen peroxide solution, extracted with toluene, washed with water, and then the toluene was distilled off. The obtained solid was recrystallized from hexane to obtain 7.0 g of the following compound (f).

F O-0-OCO-0 (f) 5.6 g of compound (f) obtained in ■■ was dissolved in 70 ml of acetic acid, and 2 ml of sulfuric acid, 1.1 g of metaperiodic acid,
Then, 2.4 g of iodine was added thereto, and the mixture was stirred at 90° C. for 10 hours. After cooling, the reaction mixture was poured into 200 ml of ice water, excess iodine was reduced with sodium bisulfite, and the precipitated solid was collected by filtration. By recrystallizing this from toluene, 3.5 g of the following compound (g) was obtained.

+-0-6-oco-0 (g) 3.5 g of the compound (g) obtained in
tnl and added with sodium hydroxide l. og was added thereto, and the mixture was heated under reflux for 1 hour. After cooling, the ethanol was distilled off and the resulting solid was dissolved in 80 ml of water. Carbon dioxide gas was blown into this solution, and the precipitated solid was collected by filtration to obtain 2.4 g of the following compound (h).

F 1 -0-0-OR (h) 2.4 g of compound (h) obtained in ■■ was added to 20 ml of dimethyl sulfoxide.
Dissolved in sodium hydroxide aqueous solution (1.0g
/10ml) and 1.2g of 1-promobentane were added, and the mixture was stirred at 65°C for 5 hours. After cooling, the reaction mixture was extracted with hexane and washed twice with water. By distilling off hexane, 2.6 g of the following compound (i) was obtained.

F 1-o-o-oc5H11 (i) 3- obtained in ■■
n-hexyloxy-6-ethynylpyridazine 0.88
and 1.5 g of compound (i) obtained in steps 1 to 2 in 30 ml of triethylamine, 24 mg of bistriphenylphosphine palladium dichloride and copper iodide (I
) was used to react for 3 hours under a nitrogen atmosphere.

After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. The toluene layer was washed with hydrochloric acid and water, then subjected to silica gel ram treatment, and then recrystallized twice with ethanol to obtain compound No. 17 in Table 1, which is a compound of the present invention.
0.83 g of compound B was obtained. The IR spectrum, H-NMR spectrum, and F-NMR spectrum of the above compound are shown in FIG. 16, FIG. 17, and FIG. 18, respectively.

Elemental analysis values: Theoretical value (%) C: 75.65 8: 7.17 N: 6.09 F: 4.13 Actual value (%) C: 75.79 II: 7.03 N: 5.95 F : 4.32 Example 8 - Preparation of compound No. 210 in Table 1 ■ 6-Bromo-2-naphthol was dissolved in 300 ml of dimethyl sulfoxide, and sodium hydroxide solution (9.0 g of sodium hydroxide, 2 oml of water was added and stirred until a homogeneous solution was obtained. Next, 37.0 g of n-hexyl bromide was added and stirred at room temperature for 3 days. The reaction solution was poured into 1.5 liters of ice water and extracted three times with hexane. After washing the hexane layer with water, hexane was removed and recrystallization was performed with methanol to obtain 54.4 g of 2-n-hexyloxy-6-promonaphthalene.

13.0 g of 2-n-hexyloxy-6-promonaphthalene obtained in ■■ and 4,3 g of 3-methyl-1-butyn-3-ol were added to 150 mI of triethylamine as a catalyst, and 1 g of bistriphenylphosphine palladium dichloride was added.
20 mg of iodized steel (I), 30 mg of triphenylphosphine 1, and 80 mg of triphenylphosphine were reacted for 6 hours at reflux temperature under a nitrogen atmosphere. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. After washing the toluene layer with IN hydrochloric acid and water, remove the moisture from the toluene layer.
62- After removal, 3.5 g of powdered sodium hydroxide was added and heated under reflux for 1 hour. After cooling, toluene was removed after washing with water. The obtained black oil was recrystallized with methanol to obtain 5.6 g of 6-n-hexyloxy-2-ethynylnaphthalene.

2.0 g of 2-n-hexyloxy-6-ethynylnaphthalene obtained in step 2 and 1.78 g of 3-n-hexyloxy-6-chloropyridazine obtained in Triphenylphosphine palladium dichloride 100mg, copper(I) iodide 25
The mixture was refluxed for 5 hours under a nitrogen atmosphere using 50 mg of triphenylphosphine 1 and 50 mg of triphenylphosphine 1. After the reaction was completed, triethylamine was removed and the mixture was extracted with toluene. 1. The toluene layer was washed with hydrochloric acid water, washed with water, and subjected to silica gel ram treatment, and then recrystallized three times with ethanol to obtain compound No. 210 in Table 1, which is a compound of the present invention.
38g was obtained. ■R spectrum and H- of the above compound
The NMR spectra are shown in FIGS. 19 and 20, respectively.

Elemental analysis values: Theoretical value (%) Actual value (%) C: 78.14 C: 78.28H: 7.9
1 H: 7.73 N: 6.51
N: 6.32 Example 9 Preparation of compound No. 216 in Table-2 Into ethanol 30×1 N1 in Table-1 obtained in Example 7
78 compound 0.5g, 5% palladium carbon 10
mg was added thereto, and hydrogenation was performed under reflux temperature and normal pressure.

After confirming that no hydrogen was absorbed, the catalyst was removed by filtration, and the mixture was cooled to room temperature. The obtained crystals were recrystallized again from ethanol to obtain 0.38 g of white crystal compound No. 216 in Table 2, which is the compound of the present invention. The IR spectrum, H-NMR spectrum, and F-NMR spectrum of the above compound are shown in FIG. 21, FIG. 22, and FIG. 23, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 7
5.00 C: 75.21H: 7.97
H: 7.76N: 6.03
N: 5.94F: 4.10F: 4.
05 The phase transition temperatures of the compounds obtained in Examples 1 to 9 are shown in Table-
Shown in 3.

Table-3 (1) 1651 Each symbol in Table 3 represents the following phase.

Cry Crystalline phase S1 Identified Smectic phase S, Smectic A phase So Smectic C phase N Nematic phase Iso No phase in which an isotropic liquid phase exists ( ) Represents a monotropic phase [Effects of the invention] The present invention is novel The present invention provides smectic liquid crystals useful as components of smectic C liquid products and smectic C liquid crystal compositions, and these smectic liquid crystals have the following notable 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 -66 negative in a liquid crystal composition.

(2) Since it changes directly from an isotropic liquid phase to a smectic C phase or from a nematic phase to a smectic C phase, it has a large tilt angle and is very useful as a component for adjusting the tilt angle.

(3) Since there is no liquid crystal phase on the lower temperature side than the smectic C phase, the temperature range of the smectic C phase can be expanded by mixing, which is very useful.

(4) Although it has a two-ring structure, it has a high upper limit temperature in the smectic C phase temperature range, so when it is added to a liquid crystal composition with a low upper limit temperature in the smectic C phase temperature range, it can be used without increasing the viscosity. It is very useful as it can raise the upper limit temperature.

(5) Because the bond in the skeleton is a rigid acetylene bond,
Good distribution.

(6) Liquid crystals containing naphthalene rings also have good alignment properties due to their rigid skeletons, and are extremely useful as components for improving the alignment properties of practical liquid crystal compositions even if they do not themselves exhibit a smectic C phase. It is.

(7) It has a lower viscosity than phenylbenzoate-based Smectic C liquid crystal.

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

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

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

(11)} Ran-based optically active substance (tolan-based dopant)
Because their structures are very similar, they have excellent compatibility with these compounds.

(12) Since the liquid crystal compound of the present invention having a triple bond has a high birefringence, it can be added not only to smectic C liquid crystal compositions but also to nematic liquid crystal compositions to reduce the thickness of liquid crystal display cells. The response speed can be increased by

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 and 5 respectively show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 2.
The IR and H-NMR of the compound obtained in
7 and 8 respectively show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 3, and FIGS. 9 and 10 respectively show the compound obtained in Example 4. 11, 12 and 13 respectively show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 5, and FIGS. Each figure shows Example 6.
The IR and H-NMR of the compound obtained in
Figures 6, 17 and 18 respectively show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 7, and Figures 19 and 20 respectively show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 8. Showing IR and H-NMR of the compound,
FIG. 21, FIG. 22, and FIG. 23 are respectively Example 9.
IR, H-NMR and F-NMR of the compound obtained in
The spectrum is shown. -69- -1018- One sign square root 8 - ZN{3b4 (..ib)

Claims (1)

[Claims] 1. General formula R-X_1-▲ Numerical formulas, chemical formulas, tables, etc.▼-Y-
A-X_2-R' (1) [In the formula, R and R' have 1 to 1 carbon atoms
18 alkyl groups, X_1 and X_2 are single bonds (direct bonds), -O--S- or -C≡C-, Y is -CH_2CH_2- or -C≡C-, and A is fluorine 1,4 which may be substituted with an atom or a chlorine atom
-phenylene group, 4,4'-biphenylene group (one or two CH groups present in these groups may be replaced by N) or 2,6-naphthylene group (-▲ , chemical formulas, tables, etc.▼- indicates a pyridazine ring [▲Mathematical formulas, chemical formulas, tables, etc.▼])
] Pyridazine-based liquid crystal compound.