JP2001302580A - Phenylacetylene compound having alkoxy group in molecule, liquid crystal composition and liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenylacetylene compound having large refractive index anisotropy, stable, easily mixable with other liquid crystals, usable as a material for composing liquid crystal devices such as a STN-type liquid crystal device and a PDCL-type liquid crystal device, and to provide a liquid crystal composition and a liquid crystal device each using the same. SOLUTION: The phenylacetylene compound is represented by formula (1) and the liquid crystal composition and the liquid crystal device are each provided by using the composition. [A1 to A12 are each H, F or the like independently and at least one of them is an aloky; R1 and R2 are each H, F, CN, SF5 or the like; and q is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as a constituent material of a liquid crystal display device or a compounding component of a liquid crystal composition, a novel phenylacetylene compound having an alkoxy group in a skeleton, a liquid crystal composition containing the same, and a liquid crystal composition containing the same. The present invention relates to a used liquid crystal element.

[0002]

2. Description of the Related Art In recent years, higher performance of liquid crystal display elements has become indispensable with the progress of the information society. As the liquid crystal composition, a material having a large refractive index anisotropy is required to achieve physical properties such as higher speed and higher performance. Tolan compounds are known as liquid crystals having relatively large refractive index anisotropy [Mol. Cryst. Liq.
Vol. 233 (1973)], the refractive index anisotropy was about 0.2, which was not a satisfactory size. Further, a compound (2) represented by the following formula has been developed (JP-A-2-83340).
Publication).

[0003]

Embedded image (In the formula, Alkyl represents an alkyl group.) This compound (2) has a refractive index anisotropy of 0.3 or more, but is not practical because of poor compatibility with other liquid crystals. Therefore, a compound (3) represented by the following formula has been developed for the purpose of improving the compatibility with other liquid crystals (Japanese Patent Application Laid-Open No.
-216841).

[0004]

Embedded image (Wherein, R represents an alkyl group, Y represents R, a fluorine atom,
A chlorine atom, a bromine atom, an iodine atom or a cyano group,
H ^{1 to} H ¹² represent a hydrogen atom, a fluorine atom or a chlorine atom
(However, at least one of H ^{1 to} H ¹² is a fluorine atom or a chlorine atom). This compound (3) was improved from the above compound (2) in compatibility with other liquid crystals, but was not necessarily sufficient in refractive index anisotropy.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phenylacetylene compound which has a large refractive index anisotropy, is easily mixed with other liquid crystals, and has more advantageous light stability. It is an object of the present invention to provide a liquid crystal composition using the same and a liquid crystal element using the same, which can be used for an optical shutter or a display element.

[0006]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a certain phenylacetylene compound has a sufficiently large refractive index anisotropy. Was completed. That is, according to the present invention, there is provided a phenylacetylene compound represented by the formula (1).

[0007]

Embedded image (Wherein, A ^{1 to} A ¹² each independently represent a hydrogen atom, a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, or a
Represents an alkyl group which may be substituted by 10 fluorine atoms, at least one of which is an alkoxy group; R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a cyano _{group, -SF 5, -NCS, 4-} R 3 - ( cycloalkyl)
Group, 4-R ³ - (cycloalkenyl group) or R ⁴ - (O) indicating the q group (wherein, R ³ is 1 the number hydrogen atom or a straight or branched carbon atoms which may be substituted with a fluorine atom And R ⁴ represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom, and q represents 0 or 1). According to the present invention, in the above formula (1), A ⁴ , A ⁵ ,
The phenylacetylene compound is provided, wherein at least one selected from the group consisting of A ⁹ and A ¹⁰ is an alkoxy group. Further, according to the present invention, there is provided a liquid crystal composition comprising at least one compound represented by the above formula (1). Further, according to the present invention, there is provided a liquid crystal element characterized in that the liquid crystal composition is sandwiched between a pair of electrode substrates.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The phenylacetylene compound of the present invention has the formula (1)
It is a compound represented by these. In the formula (1), A ^{1 to} A ¹²
Are each independently a hydrogen atom, a fluorine atom, a carbon number of 1 to 1
0 represents an alkoxy group or an alkyl group which may be substituted by a fluorine atom having 1 to 10 carbon atoms, and represents at least 1
One is an alkoxy group. At least one of A ^{1 to} A ¹² is an alkoxy group, and among them, it is preferable that at least one selected from the group consisting of A ⁴ , A ⁵ , A ⁹ and A ¹⁰ is an alkoxy group.

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, —SF ₅ ,
NCS, 4-R ³ - shows the (O) q group - (cycloalkyl) group, 4-R ³ - (cycloalkenyl group) or R ^4. Where R
³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a linear or branched fluorine atom,
R ⁴ represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by a fluorine atom. q represents 0 or 1

Specific examples of R ¹ and R ² include, for example, hydrogen atom; fluorine atom; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Alkyl groups such as octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like, and fluoroalkyl groups in which these are substituted by fluorine atoms (for example, trifluoromethyl group); methoxy group, ethoxy group, propoxy group, butoxy group , A pentyloxy group, a hexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, an alkoxy group such as a dodecyloxy group, and a fluoroalkoxy group in which these are substituted with a fluorine atom
(E.g., a methoxy group substituted with 1 to 3 fluorine atoms, an ethoxy group substituted with 1 to 5 fluorine atoms);
Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, octyloxymethyl group, nonyloxymethyl group, decyloxymethyl group, methoxyethyl group, Ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, octyloxyethyl group, nonyloxyethyl group, decyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, Butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, Hexyloxybutyl group, heptyloxybutyl group, octyloxybutyl group, methoxypentyl group, ethoxypentyl group, propoxypentyl group, butoxypentyl group, pentyloxypentyl group, Hexyl oxy pentyl group, an alkoxyalkyl group, and fluoroalkoxy group they have been substituted with fluorine atoms such as heptyloxy pentyl group; a 2-methylpropyl group, 2-methylbutyl group, 3-
A branched alkyl group such as a methylbutyl group and a 3-methylpentyl group and a fluorobranched alkyl group in which these are substituted with a fluorine atom; a 2-methylpropyloxy group, a 2-methylbutyloxy group, a 3-methylbutyloxy group, A branched alkyloxy group such as a 3-methylpentyloxy group and a fluorobranched alkyloxy group substituted with a fluorine atom; 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-butyl Cyclohexyl group, 4-pentylcyclohexyl group,
4 such as 4-hexylcyclohexyl, 4-heptylcyclohexyl, 4-octylcyclohexyl, 4-nonylcyclohexyl, 4-decylcyclohexyl, etc.
-Alkyl-cycloalkyl groups and 4-fluoroalkyl-cycloalkyl groups substituted with a fluorine atom; 4-alkyl-cycloalkenyl groups such as 4-propylcyclohexenyl group and 4-pentylcyclohexenyl group, and An atom-substituted 4-fluoroalkyl-cycloalkenyl group; a cyano group; -SF ₅ ;-
NCS and the like.

Specific examples of the phenylacetylene compound represented by the formula (1) include a compound represented by the following structural formula. However, R ¹ and R ² are preferably, but not limited to, the groups listed above.

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

The phenylacetylene compound of the present invention can be synthesized by utilizing ordinary organic synthetic means.
For example, it can be obtained by combining the reactions described in “Organic synthesis pioneered by transition metals” (by Jiro Tsuji, Doujin Kagaku). Specifically, a compound represented by the formula (IM-1) and a compound represented by the formula
The compound can be produced by reacting the compound represented by (IM-2) with or without copper iodide in the presence of a palladium catalyst and a base such as triethylamine.

[0017]

Embedded image (In the formulas (IM-1) and (IM-2), A ^{1 to} A ¹² , R
¹ and R ² have the same meaning as in formula (1). X represents _{I, Br, Cl, -OSO 2} CH 3, a -OSO ₂ CF ₃ or _{-OSO 2 -C 6 H 4 -CH 3} . The compound represented by the formula (IM-1) is, for example, a compound represented by the formula (M-1)
After coupling the compound represented by the formula (M-2) with a compound represented by the formula (M-2), 3-methyl-1-butyn-3-ol is added to a palladium catalyst in the presence or absence of copper iodide. It can be produced by reacting in the presence of a base such as triethylamine and further reacting in the presence of a base such as potassium hydroxide.

[0018]

Embedded image (In the formulas (M-1) and (M-2), A ¹ , A ^{3 to} A ⁵ , A
^{9 to} A ¹² and R ¹ have the same meaning as in formula (1). Use of compound (IM-2) in a reaction to obtain a phenylacetylene compound represented by formula (1) from a compound represented by formula (IM-1) and a compound represented by formula (IM-2) The amount is usually 0.3 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to compound (IM-1).

As the palladium catalyst used in the above reaction, palladium chloride, palladium acetate, palladium / carbon, triphenylphosphine palladium complex (for example,
Tetrakistriphenylphosphine palladium, dichlorobistriphenylphosphine palladium, etc.). The amount of the palladium catalyst used is the same as that of the compound (IM-2)
Is usually 0.0001 to 1 equivalent, preferably 0.001 to 0.1 equivalent. The amount of copper (I) iodide added as an additive depends on the amount of the starting compound (IM-
0 to 1 equivalent, preferably 0 to 0.1 equivalent to 2).
One equivalent. The base used in this reaction includes alkali metal carbonate, carboxylate, alkoxide, hydroxide, or triethylamine, diisopropylethylamine, tri-n-butylamine, tetramethylethylenediamine, 1,8-diazabicyclo [5.
4.0] undecene-7,1,5-diazabicyclo [4.
3.0] Nonene-5, pyridine, N, N-dimethylaminopyridine, dimethylaniline, N-methylmorpholine, N-methylpiperidine and the like.
Preferred are tertiary amines such as triethylamine. The amount of the base to be used is generally 1 to 1 based on compound (IM-2).
The equivalent is 00 equivalents, preferably 1 to 20 equivalents. The reaction temperature of the above reaction is usually −20 to 200 ° C., preferably 3
0-150 ° C. If necessary, for example, acetonitrile, tetrahydrofuran, ethyl acetate, N, N-dimethylformamide, hexamethylphosphorylamide, N
-Methylpyrrolidone, N, N-dimethylimidazolidinone, benzene, toluene and the like can also be used as the solvent. The amount of the solvent used is not particularly limited and can be appropriately selected.

The compound represented by the formula (1) can be obtained, for example, by converting a compound represented by the formula (IM-3) and a compound represented by the formula (IM-4) in the presence of copper iodide. In the absence of a palladium catalyst and a base such as triethylamine.

[0021]

Embedded image (In the formulas (IM-3) and (IM-4), A ^{1 to} A ¹² , R
¹ and R ² have the same meaning as in formula (1). X represents _{I, Br, Cl, -OSO 2} CH 3, a -OSO ₂ CF ₃ or _{-OSO 2 -C 6 H 4 -CH 3} . )

The compound represented by the formula (IM-3) can be produced, for example, by coupling a compound represented by the formula (M-3) with a compound represented by the formula (M-4). .

Embedded image

The compound represented by the formula (IM-3) and the compound represented by the formula (IM
In the reaction for obtaining a phenylacetylene compound represented by the formula (1) from a compound represented by the formula
The amount of -3) to be used is generally 0.3 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to compound (IM-4). As the palladium catalyst used in the above reaction,
The same catalyst as that used in the reaction between (IM-1) and (IM-2) is used. The amount of these palladium catalysts to be used is generally 0.0001 to 1 based on compound (IM-4).
It is double equivalent, preferably in the range of 0.001 to 0.1 equivalent. The amount of copper (I) iodide to be added as an additive is usually 0 to 1 equivalent, preferably 0 to 0.1 equivalent, relative to the raw material compound (IM-2). The base used in this reaction includes alkali metal carbonate, carboxylate, alkoxide, hydroxide, or triethylamine, diisopropylethylamine, tri-n-butylamine, tetramethylethylenediamine, 1,8-diazabicyclo [5. 4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, pyridine, N, N-
Organic bases such as dimethylaminopyridine, dimethylaniline, N-methylmorpholine, N-methylpiperidine and the like can be mentioned. Preferred are tertiary amines such as triethylamine. The amount of the basic substance to be used is generally 1 to 100 equivalents, preferably 1 to 20 equivalents, relative to compound (IM-4). The reaction temperature is usually 20-200 ° C, preferably 30-150 ° C. If necessary, for example, acetonitrile, tetrahydrofuran, ethyl acetate, N, N-dimethylformamide, hexamethylphosphorylamide,
A normal solvent which is inert to the reaction, such as N-methylpyrrolidone, N, N-dimethylimidazolidinone, benzene, toluene, can also be used as a reaction solvent. The amount of the solvent used is not particularly limited and can be appropriately selected.

The liquid crystal composition of the present invention contains at least one phenylacetylene compound represented by the formula (1) as a compounding component. The other components to be mixed are not particularly limited, but a compound exhibiting a liquid crystal phase or a composition thereof is preferable. In the liquid crystal composition of the present invention, the blending ratio of the phenylacetylene compound represented by the formula (1) is in the range of 0.1 to 99.9% by weight, preferably 1 to 99% by weight in the liquid crystal composition. . The liquid crystal composition of the present invention may contain one or more chiral compounds as a twisting agent. The chiral compound is not particularly limited,
Preferably, the following compounds can be exemplified.
(However, * in the examples represents an asymmetric carbon).

[0025]

Embedded image

In the liquid crystal composition of the present invention, the blending ratio of the chiral compound can be appropriately selected depending on the blending composition and the like, and is not particularly limited.

The liquid crystal display element of the present invention is not particularly limited as long as the liquid crystal composition is sandwiched between a pair of electrode substrates, and may have the same configuration as a known liquid crystal display element. The type and form of the electrode are not particularly limited, and a known electrode or the like can be used. Further, the production of the liquid crystal display element of the present invention can be performed in the same manner as the production of a normal liquid crystal display element, and other elements can be appropriately added.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 In a flask equipped with a stirrer and a thermometer, 9.60 g of the following intermediate (M1-1) and dichlorobis
(Triphenylphosphine) palladium (0.29 g), triethylamine (6.63 g) and N, N-dimethylformamide (DMF) (57.6 g) were charged and the temperature was raised to 60 ° C.
Thereafter, 3.48 g of the following intermediate (M1-2) was added to DMF7.
A solution dissolved in 0 g was added dropwise, and the mixture was stirred at 60 to 65 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ethyl acetate and hexane, and washed with water. The organic layer was separated, washed twice with water, and then concentrated.
The obtained residue was purified by silica gel chromatography using a mixture of hexane / ethyl acetate = 10/1 (volume ratio) and 0.1% by mass of triethylamine as a mobile phase. Further, recrystallization was repeated with ethanol and hexane to obtain 4.76 g of the desired compound. As a result of measuring the obtained compound by ¹ H-NMR spectrum, it was a compound (1-1) represented by the following structural formula.

[0029]

Embedded image

The intermediates (M1-1) and (M1-2) were obtained by synthesizing as follows.

Embedded image

The ¹ H-NMR spectrum data of the compound (1-1) was as follows. ¹ H-NMR (δ): 0.88 (t, 3H, J = 7.3 Hz), 0.93 (t, 3H, J =
7.3Hz), 1.20-1.40 (m, 6H), 1.53-1.71 (m, 4H), 2.59 (t, 2
H, J = 7.1Hz), 2.61 (t, 2H, J = 7.1Hz), 3.93 (s, 3H), 7.03-
7.18 (m, 6H), 7.42-7.48 (m, 5H) When the phase sequence of the compound (1-1) was evaluated by observation with a polarizing microscope, it showed a crystal phase at less than 86 ° C,
A nematic phase was exhibited in the range of 8 ° C, and an isotropic phase was exhibited above 108 ° C. Therefore, it is understood that this compound is a liquid crystal compound. Further, when the compound (1-1) was added to the nematic composition MJ931381 (manufactured by Merck Japan) at 10% by weight and the refractive index anisotropy Δn measured was extrapolated by the concentration ratio, Δn was obtained. It was a very large 39. Note that Δn was measured with an Abbe refractometer. The measurement was performed at a measurement temperature of 20 ° C. and a measurement wavelength of 589 nm.

[0032]

Industrial Applicability The phenylacetylene compound having an alkoxy group in the skeleton of the present invention and the liquid crystal composition using this compound have a large refractive index anisotropy, are stable, and are easily mixed with other liquid crystals. It is particularly useful as a material constituting a liquid crystal element typified by a super twisted nematic liquid crystal element and a PDLC (polymer-dispersed liquid crystal) liquid crystal element.

Continued on the front page (72) Inventor Chizu Sekine 6 Kitahara, Tsukuba, Ibaraki Pref. Within Sumitomo Chemical Co., Ltd. (72) Inventor Koichi Fujisawa 6 Kitahara, Tsukuba, Ibaraki Pref. Sumitomo Chemical Co., Ltd. (72) Inventor Kazunori Iwakura Osaka 2-10-1, Tsukahara, Takatsuki-shi, Futo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Masayoshi Minami 2-10-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AB64 GP03 4H027 BB04 BB11 BD01 BD07 BD24 CE01 CE03 CE04 CE05 CU01 CU03 CU04 CU05 DP01 DP03 DP04 DP05

Claims (4)

[Claims] 1. A phenylacetylene compound represented by the formula (1). Embedded image (Wherein, A ^{1 to} A ¹² each independently represent a hydrogen atom, a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, or a
Represents an alkyl group which may be substituted by 10 fluorine atoms, at least one of which is an alkoxy group; R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, a cyano _{group, -SF 5, -NCS, 4-} R 3 - ( cycloalkyl)
Group, 4-R ³ - (cycloalkenyl group) or R ⁴ - (O) indicating the q group (wherein, R ³ is 1 the number hydrogen atom or a straight or branched carbon atoms which may be substituted with a fluorine atom And R ⁴ represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom, and q represents 0 or 1). ) 2. In the formula (1), A ⁴ , A ⁵ , A ⁹ and A
^At least one selected from the group consisting of ¹⁰ has 1 carbon atom
2. An alkoxy group having from 10 to 10.
The phenylacetylene compound according to the above. 3. A liquid crystal composition comprising at least one compound represented by the formula (1) according to claim 1 or 2. 4. A liquid crystal device comprising the liquid crystal composition according to claim 3 sandwiched between a pair of electrode substrates.