JPS6354336A - Liquid crystal compound and composition - Google Patents

Abstract

NEW MATERIAL:A liquid crystal compound of formula I (R is 4-18C alkyl; one of Y1 and Y2 is F-substituted phenylene or biphenylene and the other is phenylene or biphenylene which may be substituted with F; X is COO, OCO or O; R* is optically active group containing asymmetric carbon atom). USE:Useful as a component of a liquid crystal composition. It has low viscosity, ready handleability and high stability to heat and moisture. A high-speed display or high-speed printing can be carried out by using the compound as a component of a display element or a printer head. It exhibits broad working temperature range. PREPARATION:The compound of formula I can be produced by reacting an iodine compound of formula II (e.g. p-n-alkyloxy-fluoroiodo-benzene) with propargyl alcohol in the presence of cuprous iodide and a palladium catalyst, treating the reaction product with manganese dioxide and a caustic alkali and reacting the treated product with the compound of formula III in the presence of cuprous iodide and a palladium catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to liquid crystal compounds and liquid crystal compositions.

[Prior Art] In recent years, ferroelectric liquid crystals have been actively researched in various fields because they have much faster response speed than conventional nematic liquid crystals and also have a memory effect. is being expanded. For example, on page 175 of the abstract of the 11th Liquid Crystal Symposium, a ferroelectric liquid crystal having a biphenyl/ester/phenyl skeleton is announced.

[Problems to be Solved by the Invention] However, since such materials have high viscosity, the response speed is slow for use as materials for optical elements such as display elements and printer heads, causing practical difficulties.

[Means for solving problems] That is, the present invention general formula % formula % (1) [In the formula, R is an alkyl group having 4 to 18 carbon atoms; Yl.

One of Yl is a phenylene or biphenylene group substituted with a fluorine atom, the other is a phenylene or biphenylene group optionally substituted with a fluorine atom; X is -coo-
, -oco- or -O-: R is an optically active group containing an asymmetric carbon atom. ] A liquid crystal compound represented by the following (first invention); and a liquid crystal compound represented by the general formula (1
) A liquid crystal composition exhibiting a chiral smectic phase (second invention), characterized by containing at least one liquid crystal compound represented by (a) as a compounding component.

In general formula (1), examples of R include hexyl, 2-octyl, undecyl, dodecyl, and octadecyl groups.

The phenylene or biphenylene group substituted with a fluorine atom of Yl or Yz includes a phenylene or biphenylene group in which one or more (preferably 1 or 2, particularly preferably 1) hydrogen atoms are substituted with a fluorine atom. Specific examples thereof include those shown in Table 1.

Table 1 R1 is a branched alkyl group having 4 to 8 carbon atoms,
For example, CH3 1-methyl70H/L44: -C"H-C2Hs
.

CH3 2-methyl7th)14: -CH2C” H-02Hs
.

Examples include halogen-substituted alkyl groups having 3 to 8 carbon atoms. Preferably a 2-methylbutyl group.

1-methylpropyl group, 1-methylbutyl group and 1-
Methylhebutyl group.

The compound of general formula (1) of the present invention can be produced by the following steps.

(1) Iodo compound (p
-n-furkyloxy-fluoroiodobenzene.

p=-n-alkyloxy-fluoroiodobifu-denyl, etc.) in the presence of cupric iodide and a palladium catalyst,
After reacting with propargyl alcohol, it is treated with manganese dioxide and caustic alkali to produce an acetylene compound represented by general formula (3); (ii) This is then treated in the presence of cupric iodide and a palladium catalyst. Then, the general formula (4)
The target compound is produced by reacting with the iodine compound represented by

RO-Yl-I + HCECCH20H general formula (
2) % formula % General formula (4) 111 → RO-Y1-CEC-Y2-X-R" general formula (
1) [wherein R, Yl, Y2. X and R are the same as in general formula (1). ] As a specific example of the compound of general formula (1), each symbol is shown in Table 2.
Examples include compounds shown in the following.

Table 2 [Note] He represents methyl.

Examples of the compound represented by the general formula (4) include: p-
Alkyl oxycarbonyl-iodobenzene, 4-alkyl oxycarbonyl-4-moniodobiphenyl [
4-(4”-iodophenyl)-benzoic!-(L-1-
Methyl) butyl ester.

4-(4”-iodophenyl)-benzoic acid-(L-1-
methyl)heptyl ester, etc.], p-alkyl-alkyl carbonyloxy-4'-iodobiphenyl, p-alkyl oxy-iodobenzene, 4-alkyl oxy-4-moniodobiphenyl (in the above, alkyl" has an optically active group) represents an alkyl or haloalkyl group).

and nuclear fluoro substituted products thereof.

The palladium catalyst used in the reactions (i) and (R) above is dichlorobis(triphenylphosphine)palladium(II) [PdC1z (P (C61-
1s >3 )2], tetrakis(triphenylphosphine)palladium(0) [Pd (P (Ce H
5)3)2].

The liquid crystal composition of the present invention contains at least one compound represented by general formula (1) as a compounding component.

The liquid crystal composition may include chiral smectic liquid crystals other than the compound of general formula (1) of the present invention, for example, Japanese Patent Application No. 1986-2.
Compounds of the general formula (1) described in the specification of Japanese Patent Application No. 05885, compounds of the general formula (1) described in the specification of Japanese Patent Application No. 1982-134406, compounds of the general formula (1) described in the specification of Japanese Patent Application No. 1982-134406,
Compound 1), 4-n-alkyloxy-4′-biphenylcarbon! -p'-(2-methylbutoxycarbonyl)phenyl ester, 4-n-alkyloxy-4'-biphenylcarboxylic acid-2-methylbutyl ester,
p-alkyloxybenzylidene-po-amino-2-
Ferroelectric liquid crystals such as chloro-propylcinnamate, p-alkyloxybenzylidene-po-amino-2-methylbutylcinnamate, and/or 4-(p-alkyloxybiphenyl-po-oxycarbonyl)
-4'-(2methylbutyloxycarbonyl)-cyclohexane, p-n-alkyloxybenzylidene-[)
It may contain conventional chiral smectic liquid crystals such as '-(2-methylbutyloxycarbonyl)anilino. It may also contain dichroic dyes such as anthraquinone dyes and azo dyes.

Examples of formulations of liquid crystal compositions are as follows.

(1) Compound of general formula (1): 30 to 100% by weight (preferably 40 to 60% by weight) (
2) Other chiral smectic liquid crystals: O~70% by weight
(Preferably 40 to 60% by weight) (3) Dichroic dye:
O ~ 5% by weight The upper limit of the temperature range showing the chiral smectic C phase (hereinafter abbreviated as Se phase) of the liquid crystal composition of the present invention (i.e., from the SC phase to the smectic A phase, chiral nematic phase, or isotropic liquid phase) (temperature that changes) is usually 60~
100″C1 and its lower limit (i.e. solid or smectic I phase, etc.).

The temperature at which the lower liquid crystal phase changes to the SC phase) is usually O~
30°C, and exhibits ferroelectricity in this range. Liquid crystals exhibiting ferroelectricity cause a light switching phenomenon when voltage is applied, and this can be used to create optical elements with fast response [for example, Japanese Patent Laid-Open Nos. 56-107216, 1987-118744, N. , A.

Clark, S1 block, Lagerw
a I I (Ragawal): Applied Ph
ysics Letter (Applied Fixtures Letter) Discipline, 899 (1980), etc.].

The liquid crystal composition of the present invention has a cell spacing of 0.5 to 10 μm.

Preferably, it can be vacuum-sealed into a liquid crystal cell of 0.5 to 3 μm, and by installing polarizers on both sides, it can be used as an optical element such as a display element or a printer head.

The above-mentioned liquid crystal cell can be created by bonding two glass substrates provided with transparent electrodes and whose surfaces have been subjected to alignment treatment with a spacer in between. The above spacer is alumina beads.

Examples include 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.

In the following, % indicates weight %.

In addition, in the following explanation, the value of phase transition temperature is accompanied by some variation depending on the measurement method and purity.

Example 1 24.5 O-fluorophenol in 35 hj7 water
g and 14.4 Q of caustic potassium were added, and after cooling to below 10°C, 55.6 g of iodine was added and stirred all day and night.

After extracting the produced oil with ether and washing with an aqueous sodium thiosulfate solution and water, the ether was distilled off, and then distilled under reduced pressure (155-157°C, 15% H (])
L, te, liquid p-iodo-〇-fluorophenol 1
6g was obtained.

3.0 g of this compound was dissolved in 30 m of dimethyl sulfoxide, 0.83 g of caustic potassium and 2.73 g of n-decyl bromide were added, and the mixture was stirred at room temperature for a day and night, then poured into water and extracted with 10 (7) hexane. Washed with water and dried. Thereafter, the hexane was distilled off through a short column packed with silica gel to obtain 3.9 g of liquid p-n-decyloxy-m-fluoroiodobenzene.

3.9 g of this compound was mixed with 0.7 g of propargyl alcohol.
9 and 9 were dissolved in triethylamine 107, and 40°Qmg of copper iodide and 85.0mg of dichlorobis(triphenylphosphine)palladium(II) were added, and after stirring day and night, the mixture was poured into water and extracted with 50d of ether. After washing with dilute hydrochloric acid, water, aqueous sodium bicarbonate solution, and water and drying, the ether was distilled off, dissolved in hexane, passed through a short column of activated alumina, and the hexane was distilled off to obtain 2.4 g of the following compound. Obtained.

n Cl0H210YI CECCH20H [wherein, Yl is the same as Yl in ■ in Table 1. ]2.4g of this compound
was dissolved in 30 m of benzene, and 2.49 m of manganese dioxide was dissolved.
1.07% of caustic potash was added, and the mixture was heated under reflux for 5 hours. After cooling, the solid matter was filtered off, the benzene was distilled off, the solution was dissolved in hexane, the hexane was distilled off through a short column of activated alumina, and the liquid (p-n-decyloxy-m-fluoro 2.0 g of phenyl)-acetylene was obtained.

2.0 g of this compound was added to 4-(4-iodophenyl)
-Benzoin! -(L-1-methyl)butyl ester 2.8
9 was dissolved in triethylamine 60W11, and 34.0 mg of copper iodide and 70.0 mg of dichlorobis(triphenylphosphine)palladium (II) were added thereto. After stirring day and night, the mixture was poured into water and extracted with 100 ml of ether. After washing with dilute hydrochloric acid, water, an aqueous sodium bicarbonate solution, and water and drying, the ether was distilled off.

Dissolved in toluene, passed through a short column of activated alumina, distilled off the toluene, and recrystallized with ethanol.
Compound 3.69 of Nα1 in Table 2 was obtained.

The structure of the compound was determined by NMR, Mass and IR if
I did K'X. The infrared absorption spectrum and H-NMR spectrum of the above compound are shown in Figures 1 and 2, respectively.
As shown in the figure.

IR: Acetylene 2210 cm-1 carbonyl HMR (CDCi 3 ) δ: 0, 85
~ 1.90 (28H, m), 4,0
4 (2H, t).

4, 19 (2H, m),
6.90 (IH, t).

7, 25 (2H, m),
7.56 (4H, S).

7, 65 (2H, d),
8.12 (28,d) Examples 2 to 4 Compounds Nα2 to 4 in Table 2 were produced in the same manner as in Example 1.

Example 5 In 20Od of dehydrated benzene, m-fluorophenol 2
0g of pyridine 209 were dissolved, and benzoyl chloride 289 was added dropwise over 2 hours under water cooling. After dripping,
After returning to room temperature and refluxing for 2 hours, it was poured into water.
After washing with dilute hydrochloric acid, water, sodium bicarbonate aqueous solution, and water,
By distilling off benzene, liquid m-fluorophenol benzoate 353 was obtained.

10.0 g of this compound was added to a mixed solvent of acetic acid, water, and sulfuric acid (1
00:20:3) It was made to react with 5.1g of iodine and 2.3g of periodic acid at 75-85 degreeC for 8 hours in 60d.

After the reaction was completed, it was poured into water, extracted with toluene, and then extracted with water.

An oily iodide was obtained by washing with an aqueous thioflt sodium solution and water, and distilling off toluene.

This product was dissolved in 100 mi of 95% ethanol together with caustic potassium 129, refluxed for 2 hours, the solvent was distilled off, then dissolved in water, carbon dioxide gas was blown in, and the produced solid was isolated. -iodo-m-fluorophenol3. I got J7.

This compound 3.09 was dissolved in 30d of dimethyl sulfoxide, 0.83 g of caustic potassium and 2.7 g of n-decyl bromide were added, and the mixture was stirred at room temperature all day and night, then poured into water and extracted with hexane iooy. Wash with water.

After drying, pass through a short column packed with silica gel column,
Distill the hexane to obtain liquid p-n-decyloxy-0.
-4.0 g of fluoroiodobenzene was obtained.

This compound 2. Otj, propargyl alcohol 0,
4g of triethylamine 1 (dissolved in 7!), add 20.0mg of copper iodide and 43.0mg of dichlorobis(triphenylphosphine)palladium (II),
- After stirring day and night, the mixture was poured into water and extracted with ether 50d. After washing with dilute hydrochloric acid, water, aqueous sodium bicarbonate solution, and water, and drying, ether was distilled off, and dissolved in hexane.
The hexane was distilled off through a short column of activated alumina to give compound 1.23 below.

n C10H210 YI C:
CCH 2 0H [wherein, Yl is the same as Yl in ■ in Table 1. ] This compound 1.29 is mixed with benzene 15 &! dissolved in
Manganese dioxide 1.29. Add 0.5g of caustic potash,
Refluxed for an hour. After cooling, the solids were filtered off, the benzene was distilled off, the solids were dissolved in hexane, passed through a short column of activated alumina, the hexane was distilled off, and the liquid (p-n-decyloxy-〇-fluoro phenyl)-acetylene1.
Obtained 0g.

1.0 g of this compound was added to 4-(4-iodophenyl)
-Benzoin! -(L-1-methyl)butyl ester 1.4
Triethylamine 307 with g! Copper iodide 'I7. Omg, dichlorobis(triphenylbosphine>palladium(II)) 35.h+g were added, and after stirring day and night, it was poured into water and extracted with ether 50a!!. Washed with dilute hydrochloric acid, water, aqueous sodium bicarbonate solution, and water. After drying, the ether was distilled off.Dissolved in toluene,
After passing through a short column of activated alumina to distill toluene off, the product was recrystallized from ethanol to obtain 1.5 g of compound No. 5 in Table 2.

Examples 6-8 Compounds NQ5-8 in Table 2 were produced in the same manner as in Example 1.

Table 3 shows the properties of these compounds [Nα1-8].

Table 3 In Table 3, each symbol has the following meaning.

K: Crystal phase.

SE book: chiral smectic C phase.

S,: smectic A phase.

SE: smectic E phase.

Ch: cholesteric phase ■ = Isotropic liquid phase.

・　: Phase exists.

- There are no two phases.

(): Monotropic transition.

Examples 9 to 11 Regarding liquid crystal compositions containing the compounds of Examples 1 to 8 [Nα1 to 8] and a known smectic liquid crystal compound [Compound A below] in the proportions shown in Table 4, the response speed was determined by the following method. was measured. The results are shown in Table 4, and the liquid crystal composition has a fast response speed and is useful.

Compound A Nidorans 4-(p-n-octoxyphenyl)cyclohexanecarboxylic 1l-p'-(2-methylbutyloxycarbonyl)phenyl ester The response rate is:
The liquid crystal composition was sealed in a liquid crystal cell with a cell spacing of 3μ, and
The measurement was performed by applying a voltage of 0V. A polyimide film was used as the spacer, and rubbing treatment was used as the orientation direction.

Table 4 [Effects of the Invention] The liquid crystal compound and liquid crystal composition of the present invention have the following remarkable features.

(1) Due to low viscosity, response to electric field is fast. As a result, when used as a display element, high-speed display is possible.
Also, when used as a printer head, high-speed printing is possible.

(2) Since the viscosity is low, it is easy to handle when assembling a liquid crystal element.

(3) Good stability against heat and moisture.

(4) It has a wider operating temperature range than conventional liquid crystal compositions exhibiting ferroelectricity.

[Brief explanation of drawings]

FIG. 1 shows an infrared absorption spectrum of the compound obtained in Example 1, and FIG. 2 shows an H-NMR spectrum of the same compound. Applicant: NEC Corporation Sanyo Chemical Industries, Ltd.

Claims (1)

[Claims] 1. General formula RO-Y_1-C≡C-Y_2-X-R^*(1) [wherein R is an alkyl group having 4 to 18 carbon atoms; Y_1, Y_2
one is a phenylene or biphenylene group substituted with a fluorine atom, the other is a phenylene or biphenylene group optionally substituted with a fluorine atom; X is -COO-, -
OCO- or -O-; R^* is an optically active group containing an asymmetric carbon atom. ] A liquid crystal compound represented by: 2. The compound according to claim 1, wherein one of Y_1 and Y_2 is a phenylene group substituted with one fluorine atom, and the other is a biphenylene group optionally substituted with one fluorine atom. 3. The compound according to claim 1 or 2, wherein R^* is an optically active 2-methylbutyl, 1-methylpropyl, 1-methylbutyl or 1-methylheptyl group. 4. General formula RO-Y_1-C≡C-Y_2-X-R^*(1) [wherein, R is an alkyl group having 4 to 18 carbon atoms; Y_1, Y_2
one is a phenylene or biphenylene group substituted with a fluorine atom, the other is a phenylene or biphenylene group optionally substituted with a fluorine atom; X is -COO-, -
OCO- or -O-; R^* is an optically active group containing an asymmetric carbon atom. ] A liquid crystal composition exhibiting a chiral smectic phase, characterized by containing at least one liquid crystal compound represented by the following as a compounding component. 5. The composition according to claim 4, wherein one of Y_1 and Y_2 is a phenylene group substituted with one fluorine atom, and the other is a biphenylene group optionally substituted with one fluorine atom. . 6. The composition according to claim 4 or 5, wherein R^* is an optically active 2-methylbutyl, 1-methylpropyl, 1-methylbutyl or 1-methylheptyl group.