JP2002030016A - Di- or triacetylene compound having side chain, liquid crystal composition containing the same, and liquid crystal element by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new di- or triacetylene compound having a large refractive index anisotropy, and capable of being easily mixed with other liquid crystals, and further to provide a method for producing the compound, a liquid crystal composition obtained by using the compound, and a liquid crystal element usable for a light shutter and displaying element, obtained by using the compound. SOLUTION: This di- or triacetylene compound is represented by general formula 1 [A1 to A12 are each independently H, F or a 1-10C alkyl or alkoxy which may be substituted with F; (n) is 0 or 1; R1 and R2 are each independently H, F, CN, SF5, NCS, 4-R3-(cycloalkyl), 4-R3-(cycloalkenyl) or R4-(O)q (R3 is H, or a linear or branched 1-12C alkyl which may be substituted with F; R4 is a linear or branched 1-12C alkyl or alkoxyalkyl which may be substituted with F, or a 3-12C alkynylalkenyl; (q) is 0 or 1, with the proviso that when R4 is an alkoxyalkyl, (q) is 1 and R1 and R2 are not simultaneously H)].

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, and has a di- or triacetylene compound having a side chain, a method for producing the same, a liquid crystal composition containing the same, and The present invention relates to a liquid crystal element using the same.

[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.
Cryst., Vol. 23, p. 233 (1973)], the refractive index anisotropy was about 0.2, which was not a satisfactory level. Further, a compound (2) represented by the following formula has been developed (JP-A-2-83340).

[0003]

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[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).

[0005]

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[Wherein, R represents an alkyl group, and Y represents
R represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a cyano group, and H ^{1 to} H ¹² each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and H ^{1 to} H ⁴ , H ⁹ to
At least one of H ¹² is a fluorine atom or a chlorine atom. ] A liquid crystalline acetylene derivative represented by the formula: This compound
(3) is better than compound (2) in terms of compatibility with other liquid crystals, but has a refractive index because a hydrogen atom on the benzene ring of the structural skeleton is replaced by a halogen atom such as a fluorine atom. Anisotropy is reduced and refractive index anisotropy is sacrificed at the expense of improved compatibility. Further, the following triacetylene compound having no side chain (R1 in Comparative Example 1) is known [J. Am. Chem. Soc. 113 6943-6
949 (1991)], however, as shown in Comparative Example 1, there was no liquid crystallinity, and it was not preferable as a liquid crystal composition component.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel di- or triacetylene compound having a large refractive index anisotropy and being easily mixed with another liquid crystal, a method for producing the same, and a liquid crystal composition using the same. It is an object of the present invention to provide an object and a liquid crystal element using the same, which can be used for an optical shutter or a display element.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that a certain di- or triacetylene compound has a sufficiently large refractive index anisotropy. The present invention has been completed. That is,
According to the present invention, general formula (1)

[0009]

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[Wherein A ^{1 to} A ¹² each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, or a carbon atom which may be substituted by fluorine; Represents 1 to 10 alkoxy groups, n is 0 or 1, R ¹ and R ² are each independently a hydrogen atom,
Fluorine atom, a cyano _{group, SF 5, NCS, 4-} R 3 - ( cycloalkyl) group, 4-R ³ - (cycloalkenyl) group or a R ⁴ - (O) represents a _q group, where R ³ is hydrogen R ⁴ represents an atom or an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched 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;
An alkyl group, an alkoxyalkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom, an alkynyl group having 3 to 12 carbon atoms, or a 3 to 12 carbon atom
And q is 0 or 1, and when R ⁴ is an alkoxyalkyl group, q = 1, and R ¹ and R ²
Are not simultaneously hydrogen atoms. And a di- or triacetylene compound (hereinafter, referred to as the present compound).

According to the present invention, there is provided a liquid crystal composition comprising at least one compound represented by the above general formula (1) (hereinafter referred to as the composition of the present invention). 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.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, specific examples of R ¹ and R ² include, for example, a hydrogen atom; a fluorine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Alkyl groups such as 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,
Alkoxy groups such as butoxy group, pentyloxy group, hexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group and dodecyloxy group, and fluoroalkoxy groups in which these are substituted with fluorine atoms (for example, 1-3 A methoxy group substituted with 1 fluorine atom, an ethoxy group substituted with 1 to 5 fluorine atoms);

Methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl, nonyloxymethyl, decyloxymethyl, methoxy Ethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group,
Pentyloxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, decyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl ,
Hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl , Octyloxybutyl group, methoxypentyl group, ethoxypentyl group, propoxypentyl group, butoxypentyl group, pentyloxypentyl group, hexyloxypentyl group, alkoxyalkyl groups such as heptyloxypentyl group and these were substituted with fluorine atoms Fluoroalkoxyalkyl group;

A branched alkyl group such as a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group and a 3-methylpentyl group; and a fluorobranched alkyl group in which these are substituted by a fluorine atom; 2-methylpropyloxy Group, 2
-Methylbutyloxy group, 3-methylbutyloxy group,
A branched alkyloxy group such as a 3-methylpentyloxy group and a fluorobranched alkyloxy group substituted with a fluorine atom; a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group;
4-butylcyclohexyl, 4-pentylcyclohexyl, 4-hexylcyclohexyl, 4-heptylcyclohexyl, 4-octylcyclohexyl, 4
-Alkyl-cycloalkyl groups such as -nonylcyclohexyl group, 4-decylcyclohexyl group and the like, and 4-fluoroalkyl-cycloalkyl groups substituted with a fluorine atom; 4-propylcyclohexenyl group, 4-pentylcyclohexenyl group And the like, and a 4-fluoroalkyl-cycloalkenyl group substituted with a fluorine atom; a cyano group; SF
₅ ; NCS and the like.

Specific examples of the compound of the present invention represented by the general 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.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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Among the compounds of the present invention, the triacetylene compound wherein n = 0 can be produced as follows. That is, the general formula (IM-1)

[0031]

Embedded image (IM-1)

Wherein A ¹ , A ² , A ³ , A ⁴ and R ¹ are
X has the same meaning as described above, and X represents an electron-withdrawing group. And a compound represented by the general formula (IM-2)

[0033]

Embedded image (IM-2)

Wherein A ⁵ , A ⁶ , A ⁷ , A ⁸ and R ² are
Represents the same meaning as above. [In the presence of a base] [hereinafter referred to as the production method (1) of the present invention].

The electron-withdrawing group X in the general formula (IM-1) is
Preferred _{as, -SO 2 R, -CN, -SOR} ,
—SR, —CF ₃ , and —CPh ₃ . Here, R represents an alkyl group, an alkynyl group, an alkenyl group, or a phenyl group, and Ph represents a phenyl group.

In the process (1) of the present invention, the compound (IM
The amount of -2) to be used is generally 0.3 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to compound (IM-1). The reaction temperature is not particularly limited as long as it is equal to or lower than room temperature (about 20 ° C.).
° C, preferably in the range of -80-0 ° C. The reaction solvent to be used is not particularly limited as long as it does not decompose by this reaction, but an ether solvent is preferable, and examples thereof include THF, diethyl ether, and dimethoxyethane. The amount of the solvent used is not particularly limited.
A specific example of the general formula (IM-1) is shown below.

[0037]

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[0038]

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[0039]

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Specific examples of the general formula (IM-2) are shown below.

[0041]

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[0042]

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[0043]

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[0044]

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Further, among the compounds of the present invention, the diacetylene compound in which n = 1 can be synthesized as follows. That is, the compound represented by the general formula (IM-1) and the compound represented by the general formula (IM-3)

[0046]

Embedded image (IM-4)

Wherein A ⁵ , A ⁶ , A ⁷ and A ⁸ have the same meaning as described above. And the compound represented by the formula [2] [hereinafter, referred to as the production method (2) of the present invention].

In the process (2) of the present invention, the compound (IM
The amount of -1) to be used is generally 0.3 to 10 equivalents, preferably 1 to 4 equivalents, relative to compound (IM-3).

The reaction temperature is not particularly limited as long as it is lower than room temperature, but is usually in the range of -100 to 20 ° C, preferably -80 to 0 ° C. The reaction solvent used is
The solvent is not particularly limited as long as it does not decompose by this reaction, but an ether solvent is preferable, and examples thereof include THF, diethyl ether, and dimethoxyethane. The amount of the solvent used is not particularly limited. General formula (IM−
A specific example of 3) is shown below.

[0050]

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The composition of the present invention is a liquid crystal composition containing at least one compound of the present invention represented by the general formula (1) as a compounding component. The other components to be mixed are not particularly limited, but a compound or a composition exhibiting a liquid crystal phase is preferable. In the composition of the present invention, the compounding ratio of the compound of the present invention represented by the general formula (1) is in the range of 0.1 to 99.9% by mass, preferably 1 to 99% by mass in the liquid crystal composition.

The composition of the present invention may contain one or more chiral compounds as a twisting agent. The chiral compound is not particularly limited, but preferably the following compounds can be exemplified (however, * in the examples indicates an asymmetric carbon).

[0053]

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In the 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 device of the present invention is not particularly limited as long as the composition of the present invention is sandwiched between a pair of electrode substrates, and includes a configuration similar to that of a known liquid crystal display device. 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.

[0055]

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, 0.398 g of the following intermediate (IM1-1) dissolved in 4 ml of dry THF was added to lithium diisopropylamide (226 μl of diisopropylamine and n-butyl). Lithium (prepared by mixing 1000 μl of 1.6 mol / L hexane solution) was added at −78 ° C. After stirring this for 0.5 hour, the intermediate (IM2-1)
A solution obtained by dissolving 0.244 g in THF is slowly added,
Stir for an additional 5 minutes. Further, 251 μl of chlorophosphoric acid diethyl ester was added, and the cooling bath was removed, followed by stirring for 2 hours. The reaction was cooled again to 0-5 ° C and lithium hexamethyldisilazane (hexamethyldisilazane 96% THF
1.74 ml of the solution and 1.6 mol of n-butyllithium
/ L hexane solution (prepared by mixing 4.53 ml) was added, and the cooling bath was removed, followed by stirring at room temperature for 3 hours. Quench the reaction with aqueous ammonium chloride,
The reaction was extracted with ethyl acetate. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using n-hexane to which 2% ethyl acetate was added as a mobile phase to obtain 0.271 g of the desired compound (1-1).

[0057]

Embedded image (IM1-1)

[0058]

Embedded image (IM2-1)

[0059]

Embedded image (1-1)

NMR spectrum data of compound (1-1)
The data were as follows.¹ H-NMR (δ): 3.83 (s, 3H, OCH_Three),
6.85-6.86 (m, 2H), 7.01-7.05
(M, 2H), 7.47-7.53 (m, 4H) ¹³ C-NMR (δ): 55.37 (s, 1C, OC
H_Three), 65.85 (s, 1C, acetylleni)
c), 66.84 (s, 1C, acetylleni
c), 73.35 (s, 1, acetylenic),
74.40 (d, J = 2.1 Hz, 1C, acetyl
enic), 77.22 (s, 1C, acetylen)
ic), 79.00 (s, 1C, acetylleni)
c), 112.72 (s, 1C), 114.26 (s,
2C), 115.96 (d, J = 22.7 Hz, 2
C), 117.29 (d, J = 3.0 Hz, 1C), 1
34.72 (s, 2C), 135.01 (d, J = 8.
3Hz, 2C), 160.81 (s, 1C), 163.
22 (d, J = 252.8 Hz, 1C)

Example 2 In a flask equipped with a stirrer and a thermometer, 0.464 g of the following intermediate (IM1-2) dissolved in 4 ml of dry THF was added to lithium diisopropylamide (223 μl of diisopropylamine and n-butyl). Lithium (prepared by mixing 981 μl of 1.6 mol / L hexane solution) at −78 ° C. was added. After stirring for 0.5 hour, the intermediate (IM2-1) 0.1.
A solution obtained by dissolving 240 g in THF was slowly added, and the mixture was further stirred for 5 minutes. Further, 248 μl of chlorophosphoric acid diethyl ester was added, and the cooling bath was removed, followed by stirring for 2 hours.
The reaction was cooled again to 0-5 ° C and lithium hexamethyldisilazane (1.71 ml of a 96% THF solution of hexamethyldisilazane and 1.6 mol / L of n-butyllithium).
A solution prepared in advance by mixing 4.47 ml of a hexane solution) was added, and the cooling bath was removed, followed by stirring at room temperature for 3 hours. The reaction was quenched with aqueous ammonium chloride solution and the reaction was extracted with ethyl acetate. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using n-hexane to which 2% ethyl acetate was added as a mobile phase to obtain 0.182 g of a desired compound (1-2).

[0062]

Embedded image (IM1-2)

[0063]

Embedded image (1-2)

NMR spectrum data of compound (1-2)
The data were as follows.¹ H-NMR (δ): 3.83 (s, 3H, OCH_Three),
6.85-6.86 (m, 2H), 7.48-7.50
(M, 2H), 7.58-7.63 (m, 4H) ¹³ C-NMR (δ): 55.38 (s, 1C, OC
H_Three), 65.42 (s, 1C, acetylleni)
c), 68.10 (s, 1C, acetylleni
c), 73.20 (s, 1C, acetylleni
c), 76.51 (s, 1C, acetylleni
c), 76.81 (s, 1C, acetylleni
c), 79.75 (s, 1C, acetylleni
c), 112.48 (s, 1C), 114.31 (s,
2C), 123.68 (q, J = 544.6, 272.
0 Hz, 1C, CF3), 125.11 (d, J = 1.
6 Hz, 1C), 125.39 (q, J = 7.5, 3.
8Hz, 2C), 131.03 (q, J = 65.4, 3
2.3 Hz, 1C), 133.11 (s, 2C), 13
4.80 (s, 2C), 160.96 (s, 1C)

Example 3 In a flask equipped with a stirrer and a thermometer, 0.274 g of the following intermediate (IM1-1) dissolved in 4 ml of dry THF was added to lithium diisopropylamide (156 μl of diisopropylamine and n-butyl). Lithium (prepared by mixing 688 μl of 1.6 mol / L hexane solution) was added at −78 ° C. After stirring this for 0.5 hour, the intermediate (IM2-2) 0.1.
A solution of 227 g in THF was slowly added, and the mixture was further stirred for 5 minutes. Further, 173 μl of chlorophosphoric acid diethyl ester was added, and the cooling bath was removed, followed by stirring for 2 hours.
The reaction product was cooled again to 0-5 ° C, and lithium hexamethyldisilazane (1.2 ml of a 96% THF solution of hexamethyldisilazane) and 3.125 ml of a 1.6 mol / L hexane solution of n-butyllithium were mixed and mixed in advance. Prepared) was added, the cooling bath was removed, and the mixture was stirred at room temperature for 3 hours. The reaction was quenched with aqueous ammonium chloride solution and the reaction was extracted with ethyl acetate. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using n-hexane to which 2% ethyl acetate was added as a mobile phase to obtain 0.245 g of the desired compound (1-3).

[0066]

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[0067]

Embedded image (1-3)

The NMR spectrum data of the compound (1-3) were as follows. ¹ H-NMR (δ): 0.93 (t, J = 7.2 Hz,
_{3H, CH 3), 1.36-1.46 (} m, 4H),
1.76-1.82 (m, 2H), 3.96 (t, J =
6.7Hz, 2H, OCH ₂₎ 6.82-6.85
(M, 2H), 7.01-7.05 (m, 2H), 7.
45-7.54 (m, 4H) ¹³ C-NMR (δ): 13.97 (s, 1C), 22.
41 (s, 1C), 28.08 (s, 1C), 28.7
7 (s, 1C), 65.80 (s, 1C, acetyl
enic), 66.89 (s, 1C, acetylen)
ic), 68.11 (s, 1C , OCH 2), 73.2
4 (s, 1C, acetylenic), 74.40
(D, J = 1.6 Hz, 1C, acetylleni
c), 77.18 (s, 1C, acetylleni
c), 79.15 (s, 1C, acetylleni
c), 112.26 (s, 1C), 114.68 (s,
2C), 135.91 (d, J = 22.3 Hz, 2
C), 117.23 (d, J = 3.6 Hz, 1C), 1
34.66 (s, 2C), 134.97 (d, J = 8.
2Hz, 2C), 160.3 (s, 1C), 163.1
4d, J = 251.7 Hz, 1C)

The compound (1-3) was injected into a glass cell having a gap of 8 μm, and observed with a polarizing microscope while changing the temperature.
A nematic phase was exhibited above ℃. In addition, this compound (1
The anisotropy of the refractive index of -3) is described in "Structure and physical properties of ferroelectric liquid crystal" (Atsuo Fukuda, Hideo Takezoe, Corona (1990),
(P. 316), a very large value of 0.52 (measurement temperature; 90 ° C., measurement wavelength; 633 nm).

Example 4 In a flask equipped with a stirrer and a thermometer, 0.7 g of the following intermediate (IM3-1) dissolved in 10 ml of dry THF was added to lithium diisopropylamide (226 μl of diisopropylamine and n-butyl). Lithium (1.
6 mol / L hexane solution) (prepared by mixing 1.5 ml) at -78 ° C. Set this to 0.
After stirring for 5 hours, the intermediate (IM4-1) 0.210
g dissolved in THF was added slowly, and the mixture was further stirred for 5 minutes. Furthermore, chlorophosphoric acid diethyl ester 40
5 μl was added, the cooling bath was removed, and the mixture was stirred for 2 hours. The reaction was cooled again to 0-5 ° C and potassium t-butoxide (90
%, 1.246 g), and remove the cooling bath.
Stirred for hours. The reaction was quenched with aqueous ammonium chloride solution and the reaction was extracted with dichloromethane. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using a mixture of n-hexane and 20% dichloromethane as a mobile phase to obtain the desired compound (1-4).

[0071]

Embedded image (IM3-1)

[0072]

Embedded image (IM4-1)

[0073]

Embedded image (1-4)

The NMR spectrum data of the compound (1-4) were as follows. ¹ H-NMR (δ): 1.04 (s, 18 H, CH ₃ )
2.41 (s, 6H, CH3), 3.60 (s, 4H,
_{OCH 2), 6.85-6.88 (m,} 4H), 7.3
2 (s, 2H), 7.45-7.47 (m, 4H) ¹³ C-NMR (δ): 20.01 (2C), 26.52
_{(6C, CH 3), 31.82} (2C), 72.67
(2C, acetylenic), 77.85 (2C,
OCH2), 79.54 (2C, acetylleni)
c), 79.69 (2C, acetylenic), 8
3.60 (2C, acetylenic), 113.2
2 (2C), 114.66 (4C), 122.42 (2
C), 133.51 (2C), 134.03 (4C),
138.64 (2C), 160.40 (2C, CO)

Example 5 In a flask equipped with a stirrer and a thermometer, 1.373 g of the following intermediate (IM3-2) was dried in 15 ml of THF.
Was dissolved at −78 ° C. in a solution prepared by mixing 225 μl of diisopropylamine and 1.5 ml of n-butyllithium (1.6 mol / L hexane solution) with lithium diisopropylamide. After stirring this for 0.5 hour, the intermediate (IM4-1) 0.1.
A solution obtained by dissolving 315 g in THF was slowly added, and the mixture was further stirred for 5 minutes. Further, 607 μl of chlorophosphoric acid diethyl ester was added, and the cooling bath was removed, followed by stirring for 2 hours.
The reaction was again cooled to 0-5 ° C., potassium t-butoxide (90%, 1.87 g) was added, the cooling bath was removed and the mixture was stirred at room temperature for 3 hours. The reaction was quenched with aqueous ammonium chloride solution and the reaction was extracted with dichloromethane. This was washed with saturated saline and dried over anhydrous sodium sulfate.
The obtained crude product was purified by silica gel chromatography using a mixture of n-hexane and 15% dichloromethane as a mobile phase to obtain the desired compound (1-5).

[0076]

Embedded image (IM3-2)

[0077]

Embedded image (IM4-1)

[0078]

Embedded image (1-5)

The NMR spectrum data of the compound (1-5) were as follows. ¹ H-NMR (δ): 0.88 (t, J = 6.8 Hz,
_{6H, CH 3), 1.26-1.35 (} m, 32H, C
_{H 2), 1.41-1.46 (m,} 4H, CH 2), 1.
_{75-1.81 (m, 4H, CH 2} ), 2.41 (s,
6H), 3.96 (t, J = 6.7 Hz, 4H, OCH
₂ ), 6.83-6.86 (m, 4H), 7.32
(S, 2H), 7.45-7.48 (m, 4H) ^13C -NMR (?): 14.12 (2C), 20.01
(2C), 22.68 (2C), 25.97 (2C),
29.11 (2C), 29.34 (2C), 29.35
(2C), 29.55 (2C), 29.58 (2C),
29.63 (2C), 29.65 (2C), 31.91
(2C), 68.13 (2C, OCH 2), 72.67
(2C, acetylenic), 79.52 (2C,
acethylenic), 79.69 (2C, acet
ylenic), 83.55 (2C, acetylen)
ic), 113.31 (2C), 114.64 (4
C), 122.44 (2C), 133.54 (2C),
134.07 (4C), 138.67 (2C), 16
0.03 (2C)

The compound (1-5) was injected into a glass cell having a gap of 8 μm, and the mixture was observed with a polarizing microscope while changing the temperature. As a result, a nematic phase was observed in the range of 133 ° C. to 159 ° C. Further, when the refractive index anisotropy of this compound was measured by the same method as described in Example 3, it was as large as 0.31 (measuring temperature; 135 ° C., measuring wavelength: 633 nm).

Example 6 In a flask equipped with a stirrer and a thermometer, 0.435 g of the following intermediate (IM3-3) dissolved in 8 ml of dry THF was added to n-butyllithium (1.6 mol / mol).
0.975 ml (L hexane solution) was added at -78 ° C.
After stirring this for 0.5 hour, the intermediate (IM4-2)
A solution obtained by dissolving 0.118 g in THF is slowly added,
Stir for an additional 5 minutes. Further, 263 μl of chlorophosphoric acid diethyl ester was added, and the mixture was further stirred for 2 hours while returning to room temperature. The reaction was cooled again to 0-5 ° C., potassium t-butoxide (90%, 0.81 g) was added, the cooling bath was removed, and the mixture was stirred at room temperature for 3 hours. The reaction was quenched with aqueous ammonium chloride solution and the reaction was extracted with dichloromethane. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using n-hexane to which 25% dichloromethane was added as a mobile phase to obtain the desired compound (1-
0.18 g of 6) was obtained. The NMR spectrum data of the compound (1-6) were as described below.

[0082]

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[0083]

Embedded image (IM4-2)

[0084]

Embedded image (1-6)

¹ H-NMR (δ): 0.97 (t, J =
7.5 Hz, 6H, CH ₃ ), 1.30 (d, J = 6.
1 Hz, 6 H, CH ₃ ), 1.60-1.66 (m, 2
H) 1.72-1.78 (m, 2H), 4.33 (s
extet, J = 6.1 Hz, 2H, OCH), 6.8
2-6.85 (m, 4H), 6.82-6.85 (m,
4H), 7.43-7.46 (m, 8H) ^13C -NMR (?): 9.70 (2C), 19.13
(2C), 29.08 (2C), 72.46 (2C, a
cetylenic), 75.16 (2C, OCH),
80.34 (2C, acetylenic), 83.4
3 (2C, acetylenic), 112.96 (2
C), 115.77 (4C), 122.59 (2C),
132.31 (4C), 134.20 (4C), 15
9.31 (2C, CO) Further, compound (1-6) was injected into a glass cell having a gap of 8 μm, and observed under a polarizing microscope while changing the temperature. As a result, the nematic phase was found to be in the range of 201 ° C. to 222 ° C. Indicated. When the refractive index anisotropy of this compound was measured, it was found to be 0.46 (measuring temperature: 210 ° C., measuring wavelength: 633)
nm).

Example 7 The same procedure as in Example 5 was carried out except that the intermediate (IM3-4) was used instead of the intermediate (IM3-2), whereby the following compound (1-7) was obtained.

[0087]

Embedded image (IM3-2)

[0088]

Embedded image (1-7)

The compound (1-7) was injected into a glass cell having a gap of 8 μm, and observed with a polarizing microscope while changing the temperature. As a result, a nematic phase was observed in the range of 177 ° C. to 221 ° C. When the refractive index anisotropy of this compound was measured, it was as extremely large as 0.44 (measurement temperature: 185 ° C., measurement wavelength: 633 nm).

Example 8 The same procedure as in Example 6 was carried out except that the intermediate (IM3-2) was used instead of the intermediate (IM3-3), whereby the following compound (1-8) was obtained.

[0091]

Embedded image (1-8)

The compound (1-8) was injected into a glass cell having a gap of 8 μm, and the mixture was observed with a polarizing microscope while changing the temperature. As a result, a nematic phase was shown in the range of 237 ° C. to 271 ° C.

Example 9 The procedure of Example 4 was repeated, except that the intermediate (IM3-3) was used instead of the intermediate (IM3-1), whereby the following compound (1-9) was obtained.

[0094]

Embedded image (1-9)

The compound (1-9) was injected into a glass cell having a gap of 8 μm, and observed with a polarizing microscope while changing the temperature. As a result, a nematic phase was observed in the range of 145 ° C. to 147 ° C.

Example 10 The compound (1-3) described in Example 3 was converted to a nematic liquid crystal MJ931381 (Δn = 0.14) manufactured by Merck Japan.
(20 ° C., 589 nm), and the refractive index anisotropy was measured.
m) and a liquid crystal exhibiting a large Δn was obtained.

Comparative Example 1 In a flask equipped with a stirrer and a thermometer, 0.256 g of the following intermediate (RIM1-1) and the intermediate (RIM2-
1) To a solution obtained by dissolving 153 μl in dried THF, 0.0886 g of anhydrous methoxypotassium was added to dried THF4.
The solution dissolved in ml was slowly added at -78 ° C. -7
After stirring at 8 ° C. for 2 hours, 155 μl of trimethylsilyl chloride was added, the cooling bath was removed, and the mixture was further stirred for 2 hours. The reaction vessel was cooled again to 0-5 ° C., and lithium hexamethyldisilazane (hexamethyldisilazane 2395 μm) was cooled.
l and n-butyllithium (1.6 mol / L hexane solution) 6250 μl prepared beforehand)
Of THF was added. After stirring at room temperature for 3 hours, the reaction was quenched with an aqueous ammonium chloride solution, and the reaction product was extracted with ethyl acetate. This was washed with saturated saline and dried over anhydrous sodium sulfate. The obtained crude product was purified by silica gel chromatography using n-hexane as a mobile phase to obtain the desired compound (R1) in an amount of 0.1%.
12 g were obtained.

[0098]

Embedded image (IM1-1)

[0099]

Embedded image (RIM2-1)

[0100]

Embedded image (R1)

The NMR spectrum data of the compound (1-1) were as follows. ¹ H-NMR (δ): 7.32 to 7.36 (m, 4
H), 7.37-7.41 (m, 2H), 7.52?
7.55 (m, 4H) ¹³ C-NMR (δ): 66.44 (s, 2C, acet
ylenic), 74.41 (s, 2C, acetyl)
enic), 78.56 (s, 2C, acetylen)
ic), 120.90 (s, 2C), 128.46
(S, 4C), 129.67 (s, 2C), 132.9
4 (s, 4C) Compound R1 was crystalline at room temperature. This was injected into a glass cell having a gap of 8 μm, and observed under a polarizing microscope while changing the temperature. As a result, at 93 ° C., the crystal phase changed to a liquid phase. Further, when the temperature was lowered from the liquid phase, the temperature changed to a crystalline phase at 41 ° C. Therefore, it was found that R1 was a compound that did not take a liquid crystal phase.

[0102]

The di- or triacetylene compound of the present invention has an extremely large refractive index anisotropy and is easily mixed with other liquid crystals. For example, an STN (super twisted nematic) liquid crystal element or PDLC (polymer-dispersed liquid crystal) It is particularly useful as a material constituting a liquid crystal element represented by a) type liquid crystal element.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 41/30 C07C 41/30 43/225 43/225 C 45/68 45/68 49/84 49/84 F 253/30 253/30 255/50 255/50 255/54 255/54 C09K 19/18 C09K 19/18 G02F 1/13 500 G02F 1/13 500 // C07B 61/00 300 C07B 61/00 300

Claims (5)

[Claims] 1. A compound of the general formula (1) (1) [wherein, A ^{1 to} A ¹² each independently represent a hydrogen atom, a fluorine atom, or a carbon number of 1 to 10 which may be substituted with fluorine;
Represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms which may be substituted with fluorine, n is 0 or 1,
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom,
A cyano _{group, SF 5, NCS, 4-} R 3 - ( cycloalkyl) group, 4-R ³ - (cycloalkenyl) group or a R ⁴ -
(O) represents a _q group, wherein R ³ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms which may be substituted by linear or branched fluorine.
R ⁴ represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a straight-chain or branched fluorine atom, and a carbon atom which may be substituted by a straight-chain or branched fluorine atom. 1 to 12 alkoxyalkyl groups, 3 carbon atoms
Represents an alkynyl group or an alkenyl group having 3 to 12 carbon atoms, q is 0 or 1, q = 1 when R ⁴ is an alkoxyalkyl group, and R ¹ and R ² are hydrogen atoms at the same time. There is no. And a di- or triacetylene compound represented by the formula: 2. A compound of the general formula (IM-1) (IM-1) wherein A ¹ , A ² , A ³ , A ⁴ and R ¹ have the same meaning as described above, and X represents an electron-withdrawing group. And a compound represented by the general formula (IM-2): (IM-2) wherein A ⁵ , A ⁶ , A ⁷ , A ⁸ and R ² represent the same meaning as described above. Wherein the compound represented by the formula (1) is reacted in the presence of a base.
A method for producing a compound which is 0. 3. A compound represented by the general formula (IM-1) according to claim 2 and a compound represented by the general formula (IM-3): (IM-3) wherein A ⁵ , A ⁶ , A ⁷ and A ⁸ have the same meaning as described above. The method according to claim 1, wherein the compound represented by the formula (1) is reacted in the presence of a base. 4. A liquid crystal composition comprising at least one compound represented by the general formula (1) according to claim 1. 5. A liquid crystal device comprising the liquid crystal composition according to claim 3 sandwiched between a pair of electrode substrates.