JPH11180904A - Discotic liquid crystalline compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a liquid crystal material, an electronic material or other functional materials. SOLUTION: This compound is represented by formula I [Ar is represented by formula II (Xs are each an alkyl, hydrogen or the like, with the proviso that one of Xs is other than hydrogen; R is an alkyl, benzoyloxy or the like)]. The compound represented by formula I is obtained by providing 2-methyl-4- octyloxybromobenzene from, e.g. 4-bromo-3-metylphenol and 1-chlorooctane, then reacting the resultant compound with 3-methyl-butyn-3-ol, subsequently reacting the obtained product in the presence of t-butoxypotassium and isopropanol, then changing the prepared 4-octyloxy-2-methylphenylacetylene, hexabromobenzene, triphenylacetylene, dichlorobis(triphenylphosphine)palladium and triethylamine into a three neck flask, dissolving the charged compounds under stirring, adding copper iodide thereto and carrying out a reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel phenylethynylbenzene derivative useful as a discotic liquid crystal material, an electronic material, or another functional material.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices have been widely used in word processors, personal computers, televisions, and the like, and industrial activities such as materials and devices related thereto have been actively carried out. Active development research has also been conducted on liquid crystal compounds, which are fundamental materials of liquid crystal display materials, and many compounds have been developed. The use of these compounds is not limited to display devices but is considered for the development of various applications. In addition to rod-shaped liquid crystal compounds that have been well known and used, disc-shaped liquid crystal compounds, so-called discotic liquid crystal compounds, have recently attracted attention.

A typical discotic liquid crystal compound is described in Quarterly Chemistry Review, Vol. 22, “Chemistry of Liquid Crystals”, 60-7.
As described on page 2 (1994), for example, benzene derivatives, triphenylene derivatives, truxene derivatives, phenylethynylbenzene derivatives and the like can be mentioned. It has a structure in which a group, an alkoxy group, a substituted benzoyloxy group or the like is radially substituted as its side chain. Among them, the phenylethynylbenzene derivative is an attractive compound that is easy to form a discotic nematic phase, which is a monodomain liquid crystal phase preferable for use as an optical element or another functional material.

By the way, as is known for a rod-like compound which is a typical structure of a liquid crystal, the liquid crystal phase to be formed and the transition temperature between the phases often change remarkably due to a subtle difference in the structure. This is not limited to the rod-shaped liquid crystal compound, and the same applies to the discotic liquid crystal compound. The required liquid crystal phase and the transition temperature between the phases differ depending on the target device. Therefore, the selection range can be expanded only by preparing a wide variety of compounds, and it is possible to meet various purposes. However, many discotic liquid crystal compounds have not yet been known,
This is also true for particularly attractive phenylethynylbenzene derivatives.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel discotic liquid crystal compound useful as a liquid crystal material, an electronic material, or another functional material.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the objects of the present invention can be achieved by the following compounds. (1) A discotic liquid crystalline compound represented by the general formula (1).

[0007]

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In the formula, six Ars are the same,
It may be different. X in the formula represents an alkyl group, an alkyloxy group, a halogen atom, or a hydrogen atom. However, they may be the same or different. In addition, 1 of X
One is other than a hydrogen atom. R in the formula is an alkyl group,
Represents an alkyloxy group, an alkanoyloxy group, an alkoxycarbonyl group, a benzoyloxy group, or a cinnamoyloxy group. (2) The compound according to (1), wherein all six Ar in the formula are the same. (3) The compound according to (1) or (2), wherein three of the four Xs in the formula are hydrogen atoms. (4) The compound according to (1), (2) or (3), wherein X in the formula is a methyl group.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula, X represents an alkyl group, an alkyloxy group, or a halogen atom. X is preferably an alkyl group or an alkyloxy group, more preferably an alkyl group. Specifically, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group), an alkyloxy group (eg, a methyloxy group, an ethyloxy group, a propyloxy group) Group, butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group), halogen atom (for example, fluorine atom, chlorine atom, bromine atom,
Iodine atom).

The alkyloxy group and the alkyl group may be unsubstituted even if they are unsubstituted, by C. Hansch, A. Leo, RW Taft, Chemical Review (Chem. Rev) 1991, 91, 165-19.
It may be substituted with a substituent described on page 5 (American Chemical Society). Representative examples of the substituent further substituted include an alkoxy group, an alkyl group, an alkoxycarbonyl group, and a halogen atom. The alkyl group and the alkyloxy group preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and most preferably 1 carbon atom. In addition, among the four Xs in one Ar group, two are preferably hydrogen atoms, and more preferably three are hydrogen atoms. Specifically, an alkoxy group (for example,
Methyloxy group, ethyloxy group, propyloxy group,
Butyloxy group, pentyloxy group), alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, Butyloxycarbonyl group,
A pentyloxycarbonyl group), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and the like.

R in the formula is an alkyl group, an alkyloxy group, an alkanoyloxy group, an alkoxycarbonyl group,
It represents a benzoyloxy group or a cinnamoyloxy group. Alkyl groups, alkoxy groups, alkanoyloxy groups, alkoxycarbonyl groups, benzoyloxy groups, cinnamoyloxy groups are unsubstituted, but are not limited to C. Hansch, A. Leo, RW
Taft, Chemical Review Magazine (Chem. Rev), 1991, 9
1, pp. 165-195 (American Chemical Society), which may be substituted. Representative examples of the substituent when further substituting are an alkoxy group, an alkyl group,
Examples include an alkoxycarbonyl group and a halogen atom.
Further, the molecule may have a functional group such as an ether group, an ester group, a carbonyl group, a thioether group, a sulfoxide group, a sulfonyl group, and an amide group. Further, it may have a substituent capable of causing a polymerization reaction.
Specific examples of the substituent capable of causing a polymerization reaction include an acryloyl group, a methacryloyl group, a crotonoyl group, a vinyl ether group, and an epoxy group. Specific examples of the substituent for further substitution include an alkoxy group (for example, a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group), halogen atom (for example, fluorine atom, chlorine atom, Bromine atom, iodine atom).

R in the formula will be described in more detail. The alkyl group has 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and is, for example, an unsubstituted alkyl group (for example,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, undecanyl group, dodecanyl group), substituted alkyl group (for example, 4-
Methoxybutyl group, 6-methoxyhexyl group, 4-acryloyloxybutyl group, 6-acryloylhexyl group, 4-methacryloxybutyl group, 6-methacryloxyhexyl group).

The alkyloxy group has 2 to 3 carbon atoms.
0, preferably 2 to 20, for example, an unsubstituted alkyloxy group (for example, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group,
Nonyloxy group, undecanyloxy group, dodecanyloxy group), substituted alkyloxy group (for example, 4-methoxybutyloxy group, 6-methoxyhexyloxy group,
-Acryloyloxybutyloxy group, 6-acryloylhexyloxy group, 4-methacryloxybutyloxy group, 6-methacryloxyhexyloxy group).

The alkanoyloxy group has 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and is, for example, an unsubstituted alkanoyloxy group (for example, ethanoyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group). Group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, undecanoyloxy group, dodecanoyloxy group), substituted alkyloxy group (for example, 4-methoxybutanoyloxy group, 6-methoxy Hexanoyloxy group, 4-acryloyloxybutanoyloxy group, 6-
Acryloylhexanoyloxy group, 4-methacryloxybutanoyloxy group, 6-methacryloxyhexanoyloxy group).

The alkoxycarbonyl group has 2 to 20, preferably 2 to 20 carbon atoms and includes, for example, an unsubstituted alkoxycarbonyl group (for example, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a pentyloxy group). Carbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, undecanyloxycarbonyl group, dodecanyloxycarbonyl group), substituted alkoxycarbonyl group (for example, 4-methoxybutyloxycarbonyl) Group, 6
-Methoxyhexyloxycarbonyl group, 4-acryloyloxybutyloxycarbonyl group, 6-acryloylhexyloxycarbonyl group, 4-methacryloxybutyloxycarbonyl group, 6-methacryloxyhexyloxycarbonyl group).

The benzoyloxy group and cinnamoyloxy group preferably have a substituent at the para-position, and examples of the substituent include an alkyloxy group, an alkyl group, an alkoxycarbonyl group, an alkanoyloxy group, and a halogen atom. Is preferably an alkyloxy group. This alkyloxy group has 2 to 30 carbon atoms,
Preferred are those having 2 to 20, for example, unsubstituted alkyloxy groups (for example, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, undecayl) Nyloxy group, dodecanyloxy group), substituted alkyloxy group (for example, 4-methoxybutyloxy group, 6-methoxyhexyloxy group, 4-acryloyloxybutyloxy group, 6-acryloylhexyloxy group, 4-methacryloxy) Butyloxy group, 6-methacryloxyhexyloxy group). In addition, the ortho-position or the meta-position may be substituted in addition to the para-position substituent, and when further substituting, for example, an alkyloxy group, an alkyl group, an alkoxycarbonyl group, an alkanoyloxy group, a halogen atom And preferably an alkyloxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, more preferably 1 to 3 carbon atoms.
Is an alkyl group.

Specific examples of the substituent for further substitution include an alkyloxy group (for example, a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group), and an alkyl group (for example, a methyl group, an ethyl group) , Propyl group, butyl group, pentyl group), alkoxycarbonyl group (for example, methyloxycarbonyl group,
Ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group), alkanoyloxy group (for example, methanoyloxy group, ethanoyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy Group), halogen atom (for example, fluorine atom, chlorine atom, bromine atom,
Iodine atom). Hereinafter, specific examples of the present invention will be described. However, the scope of the present invention is not limited only to these.

[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]

The present invention will be described below in detail with reference to examples. Example (Synthesis of Compound 6) Synthesis of 2-methyl-4-octyloxybromobenzene In a three-necked flask, 6.5 g of 4-bromo-3-methylphenol, 5.17 g of 1-chlorooctane, 4.8 g of potassium carbonate and 30 ml of DMF. And stirred at 120 ° C. for 3 hours. After cooling, the reaction solution was added with ethyl acetate and washed with water. After the ethyl acetate was distilled off, the residue was purified by column chromatography to obtain 9.5 g (91%) of the desired product.

Synthesis of 4- (2-methyl-4-octyloxyphenyl) -2-methyl-3-butyn-2-ol 9.3 g of 2-methyl-4-octyloxybromobenzene was placed in a 200 ml three-necked flask. -Methyl-1-butyn-3-ol 3.92 g, triphenylphosphine 1
30 mg, 68 mg of dichlorobis (triphenylphosphine) palladium and 200 ml of triethylamine were charged,
After stirring and dissolving, 21 mg of copper iodide was added. After stirring under reflux for 2 days, the temperature was returned to room temperature, ethyl acetate was added, and the mixture was washed with water. After the ethyl acetate was distilled off, the residue was purified by column chromatography to obtain 3.15 g (34%) of the desired product.

¹ H-NMR data (CDCl ₃ ) 7.29
(D, 1H), 6.72 (d, 1H), 6.67 (d
d, 1H), 3.92 (t, 2H), 2.42 (s, 3
H), 1.7-1.9 (m, 2H), 1.65 (s, 6
H), 1.2-1.5 (m, 10H), 0.92 (t,
3H)

Synthesis of 4-octyloxy-2-methylphenylacetylene 4- (2-methyl-4-octyloxyphenyl) 2-methyl-3-butyne-2- was added to a 200 ml three-necked flask.
3.03 g of all, 2.24 g of potassium t-butoxide and 50 ml of isopropanol were charged and stirred under reflux for 3 hours. After cooling, hexane was added and washed with water. After distilling off hexane, the residue was purified by column chromatography to obtain 1.68 g (69%) of the desired product.

¹ H-NMR data (CDCl ₃ ) 7.39
(D, 1H), 6.72 (d, 1H), 6.67 (d
d, 1H), 3.95 (t, 2H), 3.21 (s, 1
H), 2.45 (s, 3H), 1.7-1.9 (m, 2
H), 1.2-1.5 (m, 10H), 0.92 (t,
3H)

Synthesis of Compound 6 In a 200 ml three-necked flask, 4-octyloxy-2-
0.80 g of methylphenylacetylene, 0.202 g of hexabromobenzene, 44 mg of triphenylphosphine,
Dichlorobis (triphenylphosphine) palladium 2
2 mg and 10 ml of triethylamine were charged and dissolved by stirring, and 22 mg of copper iodide was added. After stirring under reflux for 18 hours, the temperature was returned to room temperature, ethyl acetate was added, and the mixture was washed with water. After the ethyl acetate was distilled off, the residue was purified by column chromatography to obtain 0.23 g (41%) of the desired product.

¹ H-NMR data (CDCl ₃ ) 7.42
(D, 1H), 6.74 (d, 1H), 6.67 (d
d, 1H), 3.96 (t, 2H), 3.21 (s, 1
H), 2.45 (s, 3H), 1.7-1.9 (m, 2
H), 1.2-1.5 (m, 10H), 0.92 (t,
3H)

The phase change of the compound of the present invention by a polarizing microscope is shown below. Phase change of compound 6 When compound 6 is heated, it becomes an isotropic liquid at 83 ° C. When this isotropic liquid is cooled, it shows a texture of a discotic nematic phase at 60 ° C., and at 41 ° C., the texture disappears and becomes a crystal. As described above, it can be seen that the compound of the present invention has a significant characteristic of exhibiting liquid crystallinity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 69/54 C07C 69/54 Z 69/734 69/734 Z 69/92 69/92 C07D 303/24 C07D 303/24 C09K 19 / 18 C09K 19/18 19/34 19/34 G02F 1/13 500 G02F 1/13 500

Claims (3)

[Claims] 1. A discotic liquid crystalline compound represented by the following general formula (I). Embedded image The six Ars in the formula may be the same or different. X in the formula is an alkyl group, an alkyloxy group,
Represents a halogen atom or a hydrogen atom. However, they may be the same or different. One of X is other than a hydrogen atom. R in the formula represents an alkyl group, an alkyloxy group, an alkanoyloxy group, an alkoxycarbonyl group, a benzoyloxy group, or a cinnamoyloxy group. 2. The substituent represented by R further comprises an ether group,
2. A compound having an ester group, a carbonyl group, a thioether group, a sulfoxide group, a sulfonyl group or an amide group.
A compound as described. 3. The compound according to claim 1, wherein the substituent represented by R further has an acryloyl group, a methacryloyl group, a crotonoyl group, a vinyl ether group or an epoxy group.