JPH1053585A - Pyridinium type inonic compound derivative, its production and liquid crystal substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative useful as a thermotropic liquid substance for liquid crystal display materials, etc., by reducing the reaction product of a malonic acid diester with an alkyl halide and subsequently reacting the reduction product with pyridine-4-aldehyde. SOLUTION: A new pyridinium type ionic compound directive having a 1,3- dioxane ring basic structure and represented by formula I (R<1> , R<2> are each a 1-22C alkyl; X is a halogen). The compound of formula I is useful as a thermotropic liquid crystal substance exhibiting a smectic A phase or chiral smetic phase liquid crystal property for liquid crystal display materials including liquid crystal elements utilizing optothermal or optoelectric effects, etc. The compound of formula I is obtained by reacting an alkyl halide compound of the formula: R<1> X with a malonic acid diester, reducing the obtained compound of formula II (R<3> is a 1-3C lower alkyl), reacting the obtained diol compound of formula III with pyridine-4-aldehyde and subsequently reacting the obtained pyridine derivative of formula IV with a compound of the formula: R<2> X.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pyridinium-type ionic compound derivative having a basic structure of a 1,3-dioxane ring, a pyridinium-type ionic optically active compound derivative and a method for producing the same, and more particularly, to heat, electricity, and the like. The present invention relates to a liquid crystal material useful as a liquid crystal display material including a liquid crystal element utilizing an optical effect.

[0002]

2. Description of the Related Art Liquid crystal substances are classified into a thermotropic liquid crystal (temperature transition type liquid crystal) and a lyotropic liquid crystal (concentration transition type liquid crystal) based on a means for giving a phase transition.
These liquid crystals are classified into three types, a smectic liquid crystal, a nematic liquid crystal, and a cholesteric liquid crystal, in terms of molecular arrangement.

At present, a liquid crystal material which is practically used as an electronic material for a liquid crystal display or the like is a thermotropic liquid crystal, and has the following general formula (V)

[0004]

Embedded image (Wherein A represents an alkyl group), a cyanophenyldioxane-based liquid crystal compound represented by the following general formula (V
I)

[0005]

Embedded image (Wherein, B represents an alkyl group or an aralkyl group)
And the like are known.

[0006]

The above-mentioned cyanophenyldioxane-based liquid crystal compound and cyanophenylcyclohexane-based liquid crystal compound are exemplified by the following chemical formula (C).
As shown in (1), the molecule has a cyano group at the terminal, and the electron withdrawing property of the cyano group increases the dielectric constant in the molecular long axis direction and has a positive dielectric anisotropy.

[0007]

Embedded image

[0008] The liquid crystal compound requires a practical temperature range of -40 ° C to + 60 ° C to show the liquid crystal state.
To realize this, many liquid crystal compounds, for example, a mixed liquid crystal composition of about 10 types of liquid crystal compounds have been put to practical use. In order to drive the mixed liquid crystal compound by applying a voltage, a liquid crystal compound having a positive dielectric anisotropy is contained at a mixing ratio of about 20% of the liquid crystal composition. As the liquid crystal compound having a positive dielectric anisotropy, the above-mentioned cyanophenyl liquid crystal compound is used.

Since the driving speed of this mixed liquid crystal composition is proportional to the magnitude of the dielectric anisotropy, a compound having a large electric charge bias in the molecular long axis direction is desired. There is a demand for a liquid crystal compound having a larger charge deviation in the molecular long axis direction than the compound.

The inventor of the present invention has conducted intensive studies in view of the above points and found that the presence of ionic N ⁺ in the molecule significantly increases the bias of charges in the direction of the long axis of the molecule. And a new compound, a pyridinium-type ionic compound derivative and a pyridinium-type ionic optically active compound derivative having a basic skeleton structure of a 1,3-dioxane ring, which can have a large torque by an external force such as an electric field. Thus, the present invention has been completed.

An object of the present invention is to provide a pyridinium-type ionic compound derivative, a pyridinium-type ionic optically active compound derivative, which are promising novel compounds as high-performance liquid crystal materials, and a method for producing the same.

[0012]

The novel compounds to be provided by the present invention have the following general formula (I):

[0013]

Embedded image Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 22 carbon atoms, and X is a halogen atom. A pyridinium-type ionic compound derivative having a basic structure of a 1,3-dioxane ring It is related to.

Further, the present invention provides the following first to fourth steps.
The present invention relates to a method for producing a pyridinium-type ionic compound derivative having a basic structure of an l, 3-dioxane ring represented by the above general formula (I), which comprises a step.

(A) a compound represented by the formula: R ¹ X (wherein R ¹ and X are as defined above);

[0016]

Embedded image (Wherein, R ³ represents a lower alkyl group having 1 to ³ carbon atoms), and reacted with a compound represented by the general formula (II)

[0017]

Embedded image (Wherein R ¹ and R ³ have the same meanings as described above),

(B) Formula (I) obtained in the first step
The compound represented by the formula (I) is reduced to give a compound of the general formula (III)

[0019]

Embedded image (Wherein, R ¹ has the same meaning as described above),

(C) Formula (I) obtained in the second step
The compound represented by II) is reacted with pyridine-4-aldehyde to give a compound of the general formula (IV)

[0021]

Embedded image (Wherein, R ¹ has the same meaning as described above),

(D) Formula (I) obtained in the third step.
Reacting a compound represented by V) with a compound represented by the formula: R ² X (wherein R ² and X are as defined above),
General formula (I)

[0023]

Embedded image (Wherein R ¹ and R ² have the same meanings as described above) in the fourth step of synthesizing a pyridinium-type ionic compound derivative having a basic structure of 1,3-dioxane ring.

Further, a novel compound to be provided by the present invention has the following general formula (XI):

[0025]

Embedded image (Wherein, R ¹ represents the same or different alkyl group having 1 to 22 carbon atoms, X represents a halogen atom, and R ⁴ represents the following formula (X
Represents an optically active group represented by II).

[0026]

Embedded image Here, Y represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 10, n represents an integer of 1 to 9, and * represents an asymmetric carbon atom. The present invention relates to a pyridinium-type ionic optically active compound derivative having a basic structure of a 1,3-dioxane ring represented by the formula (1).

Further, the present invention provides the following first to fourth steps.
A method for producing a pyridinium-type ionic optically active compound derivative having a basic structure of an l, 3-dioxane ring, comprising the steps of: (A) a compound represented by the formula: R ¹ X (wherein R ¹ and X are as defined above);

[0028]

Embedded image (Wherein, R ³ represents a lower alkyl group having 1 to ³ carbon atoms), and reacted with a compound represented by the general formula (II):

[0029]

Embedded image (Wherein R ¹ and R ³ are as defined above), (b) reducing the compound represented by the general formula (II) obtained in the first step, And the general formula (III)

[0030]

Embedded image (Wherein, R ¹ has the same meaning as described above), (c) a compound represented by the general formula (III) obtained in the second step, and pyridine-4-aldehyde And reacting with the general formula (IV)

[0031]

Embedded image (Wherein R ¹ is as defined above), (d ') a compound represented by the general formula (IV) obtained in the third step, and a compound represented by the formula: R ⁴ X (where
R ⁴ and X have the same meanings as defined above), and reacted with a compound of the general formula (XI)

[0032]

Embedded image (Wherein, R ¹ and R ⁴ are as defined above)
A fourth step of synthesizing a pyridinium-type ionic optically active compound derivative having a basic structure of a 3-dioxane ring.

Further, the present invention provides a liquid crystal material comprising a pyridinium-type ionic compound derivative represented by the above general formula (I) and a pyridinium-type ionic optically active compound derivative represented by the general formula (X) as an active ingredient. It is related to.

[0034]

DETAILED DESCRIPTION OF THE INVENTION The novel compounds to be provided by the present invention are represented by the following general formula (I):

[0035]

Embedded image (Wherein R ¹ , R ² , and X have the same meanings as described above) and a pyridinium-type ionic compound derivative having a basic structure of a 1,3-dioxane ring (hereinafter, represented by the general formula (I) A compound)).

The present invention also provides a highly functional liquid crystal material characterized by the constitution of the compound represented by formula (I). The compound represented by the general formula (I) according to the present invention is a novel smectic A phase liquid crystal material which exhibits thermotropic liquid crystallinity and in which the molecular arrangement forms a vertical layer and is oriented.

In the compound represented by the general formula (I),
R ¹ and R ² are the same or different alkyl groups having 1 to 22 carbon atoms as described above. For example, lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group may be substituted with octyl group, nonyl group and decyl group. , Undecyl group, dodecyl group,
Examples thereof include a linear or branched alkyl group having up to 22 carbon atoms, such as a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, and a docosyl group. Among them, R ¹ is a linear alkyl group having 8 to 12 carbon atoms, preferably 9 to 11 carbon atoms, and R ² is preferably an ethyl group industrially.

In the general formula (I), X is Cl,
It is a halogen atom of Br or I, preferably Cl or Br, particularly Br.

In the compound represented by the general formula (I), when the alkyl group of R ¹ or R ² is increased, the regularity of the molecular arrangement is improved, but the viscosity of the liquid crystal tends to be increased. Br salt is easier to form a stable liquid crystal state than salt.

The compound represented by the general formula (I) according to the present invention includes, for example, N-ethyl-4- (5-methyl-
1,3-dioxa-2-yl) pyridinium bromide, N-ethyl-4- (5-ethyl-1,3-dioxa-2-yl) pyridinium bromide, N-ethyl-4
-(5-propyl-1,3-dioxa-2-yl) pyridinium bromide, N-ethyl-4- (5-butyl-
1,3-dioxa-2-yl) pyridinium bromide and the like, but are not limited thereto.

Another novel compound to be provided by the present invention is represented by the following general formula (XI):

[0042]

Embedded image (Wherein R ¹ , R ⁴ and X have the same meanings as described above) and a pyridinium-type ionic optically active compound derivative having a basic structure of a 1,3-dioxane ring (hereinafter referred to as “general formula (X
A compound represented by I))).

The present invention also provides a high-functional liquid crystal material characterized by the constitution of the compound represented by the above general formula (XI). The compound represented by the general formula (XI) according to the present invention is an optically active liquid crystalline compound, which is obtained by introducing an optically active asymmetric carbon atom (chiral group) into a smectic liquid crystal molecule. , Called chiral smectic liquid crystal.

The feature is that it has ferroelectricity. The ferroelectricity has excellent characteristics such as high-speed response, memory characteristics in which the alignment state of liquid crystal molecules is maintained even when voltage is removed, and bistability in which the orientation of molecules is in two stable states. Has nature.

In the compound represented by the general formula (XI), R ¹ and X are the same as those represented by the general formula (I).

R ⁴ represents an optically active group represented by the following formula (XII).

[0047]

Embedded image In the following formula (XII), Y represents 1 to 1 carbon atoms.
4, preferably an alkyl group having 1 to 2 carbon atoms.

M is an integer of 0 to 10, preferably 1 to 5,
n represents an integer of 1 to 9, preferably 1 to 5. * Represents an asymmetric carbon atom.

Specific examples of the optically active group represented by the formula (XII) for R ⁴ include the following groups.

[0050]

Embedded image

In the compound represented by the above general formula (XI), when the alkyl group of R ¹ or R ⁴ is increased, the regularity of the molecular arrangement is improved, but the viscosity of the liquid crystal tends to be increased. Br salt is easier to form a stable liquid crystal state than salt.

The compound represented by general formula (XI) according to the present invention includes, for example, N- (S)-(+)-2-methylbutyl-4- (5-decyl-1,3-dioxa-2-yl ) Pyridium bromide, N- (S)-(+)-2-
Examples include, but are not limited to, methylbutyl-4- (5-octadecyl-1,3-dioxa-2-yl) pyridium bromide.

The above general formulas (I) and (XI) of the present invention
Are represented by the following chemical formulas (D) and (E)
As shown in ( ^1), by having N ⁺ in the molecule, the bias of the charge in the long axis direction of the molecule becomes extremely large, and it is a novel compound that may have a large torque when driven by an external force such as an electric field. .

[0054]

Embedded image

Specifically, it is clear from the proton NMR spectrum that the compound represented by the general formula (I) has a large charge bias as compared with a general cyanophenyl liquid crystal compound. That is, the absorption position of the proton NMR spectrum of the hydrogen atom at the position a of the compound (D) represented by the general formula (I) of the present invention is determined by the a position of the cyanophenyl liquid crystal compound represented by the chemical formula (C). The hydrogen atom at position 'is larger than the absorption position in the proton NMR spectrum of the proton NMR spectrum and is in a low magnetic field, which is considered to be caused by the very large electron withdrawing by N ⁺ . In particular,

[0056]

## EQU1 ## Absorption of hydrogen atom of a '= 7.6 ppm Absorption of hydrogen atom of a = 8.2 ppm and 9.9 ppm.

That is, since the compound represented by the general formula (I) of the present invention has a very large bias of electric charge in the molecular long axis direction, it has a very large torque when an external force such as an electric field acts. And its usefulness as a highly functional material is very large.

Next, the process for producing the compound represented by the above general formula (I) to be provided by the present invention is as follows:
The reaction is performed by the reactions of the steps to the fourth step. (1) First step The following reaction formula (1)

[0059]

Embedded image (Wherein, R ¹ and X are as defined above. R ³ has 1 carbon atom.
A first step of synthesizing a lower dialkyl malonate compound (II) represented by the general formula (II) by a reaction represented by

(2) Second step The following reaction formula (2)

[0061]

Embedded image (Wherein R ¹ and R ³ have the same meanings as described above), and the lower dialkylmalonate compound (II) obtained in the first step is reduced to give a compound of the general formula (III)
A second step of synthesizing a 2-alkyl-1,3-propanediol compound (III) represented by

(3) Third step The following reaction formula (3)

[0063]

Embedded image (Wherein, R ¹ has the same meaning as described above), and the 2-alkyl-1,3- obtained in the second step is obtained.
The propanediol compound (III) is reacted with pyridine-4-aldehyde to give a compound represented by the general formula (IV):
A third step of synthesizing (5-alkyl-1,3-dioxa-2-yl) pyridine compound (IV),

(4) Fourth step The following reaction formula (4)

[0065]

Embedded image (Wherein R ¹ , R ² , and X have the same meanings as described above), and the 4- (5-alkyl-1,3-dioxa-2-yl) obtained in the third step is obtained. A pyridine compound (IV) is reacted with a halogen compound represented by the formula: R ² X to synthesize a compound represented by the general formula (I).
Process.

Hereinafter, the first to fourth steps will be described more specifically.

First step: This first step is a step of synthesizing a lower dialkyl-2-alkylmalonate as shown in the above reaction formula (1). That is, the alkyl halide is reacted with the dialkyl malonate in the presence of a strong base catalyst.

The catalyst is preferably an alcoholate of an alkali metal such as sodium, potassium or lithium. Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol.

The reaction temperature is from 0 to 100.
° C, preferably 20 to 50 ° C, and the reaction time is 0.5
The reaction is carried out by refluxing for 50 hours, preferably 10-20 hours. After the reaction, neutralize by the usual method,
The intermediate lower dialkyl malonate compound (II) is obtained through various operations such as washing, extraction and dehydration.

Second step: This second step is a step of synthesizing a 2-alkyl-1,3-propanediol compound (III) as shown in the above reaction formula (2). That is, the lower dialkyl malonate compound (II) obtained in the first step is subjected to a reduction treatment in a solvent containing a reducing agent to give a 2-alkyl 1,3-propanediol compound (I
II) is synthesized.

As the reducing agent, for example, AlH ₃ , LiA
lH ₄ , LiAlH ₄ —AlCl ₃ , LiAlH (OC
_{H 3) 3, NaH-LiAlH} 4, NaBH 4, LiB
Metal hydrides such as H ₄ and BH ₃ , and methanol, ethanol such as metal sodium, potassium and lithium;
Alcoholates such as propanol and butanol are preferred.

As the solvent, diethyl ether,
Ethers such as dipropyl ether, diisopropyl ether, dibutyl ether, anisole, diphenyl ether, dioxane, trioxane, furan and tetrahydrofuran, and aromatic hydrocarbons such as benzene, toluene and xylene are preferred.

The reaction conditions are as follows.
C., preferably 20-100.degree. C., and the reaction time is 0.1.
The reduction is performed under reflux for 5 to 10 hours, preferably 2 to 5 hours. The reducing agent varies depending on its type and reaction conditions, but is preferably used in an equimolar amount or more, and preferably in a range of 1.5 to 3 mol, based on compound (II).

After completion of the reaction, the unreacted reducing agent is decomposed by an ester such as ethyl acetate, and the metal generated from the reducing agent is separated from the ether layer as a water-soluble salt as an ammonium salt. Thereafter, the compound (III) is synthesized by separation, purification and dehydration according to a conventional method.

Third step: This third step is a step of synthesizing 4- (5-alkyl-1,3-dioxa-2-yl) pyridine compound (IV) as shown in the above reaction formula (3). is there. That is, the 2-alkyl-1,3-propanediol compound (III) and the pyridine-4-aldehyde are subjected to a ring closing reaction in the presence of a Lewis acid.

Examples of the Lewis acid include aromatic sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid and phosphoric acid. Compound (III) and pyridine-4
The aldehyde is reacted in a quantitative relationship near equimolar;

The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene, ether, petroleum ether, and ligroin. As the reaction conditions, the temperature varies depending on the solvent used, but the reaction is carried out at a refluxing temperature. The reaction time is 0.5 to 20 hours, preferably 2 to 10 hours. The reaction proceeds while removing. After completion of the reaction, the compound (IV) is obtained by subjecting it to separation, purification and dehydration according to a conventional method.

Fourth step: As shown in the above-mentioned reaction formula (4), this fourth step comprises N-alkyl-4- (5-alkyl-1,3 represented by the general formula (I) according to the present invention. -Dioxa-2-yl) pyridinium halide (I).

That is, in this step, the 4- (5-alkyl-1,3-dioxa-2-) obtained in the third step is obtained.
Yl) By reacting the pyridine compound (IV) with an alkyl halide, a pyridinium halide of the compound represented by the general formula (I) is synthesized.

As the solvent, a nitrile compound such as acetonitrile, propionitrile and butyl nitrile, or a solvent having a large polarity such as an alcohol such as methanol, ethanol and propanol is preferable.

The amount of the alkyl halide used for the compound (IV) varies depending on the size of the alkyl group and the difference in Cl or Br, but is often used in excess, preferably in a stoichiometric amount. 5 to 20 times the amount is used.

This reaction is carried out by refluxing in an inert atmosphere such as nitrogen at a temperature of 50 to 150 ° C., preferably 50 to 100 ° C., for a reaction time of 1 to 30 hours, preferably 5 to 24 hours. After completion of the reaction, separation, purification and drying are carried out by a conventional method to obtain the target substance of the compound represented by the general formula (I).

The structural characteristics of the novel liquid crystalline compound represented by the general formula (I) according to the present invention are as follows.
It has a positively charged nitrogen atom forming a pyridine ring connected to a dioxane ring, and has two alkyl groups as a nonpolar part. Because of such a characteristic molecular structure,
It is more excellent in liquid crystal characteristics than a conventionally known cyanophenyl-based liquid crystalline substance linked to a 1,3-dioxane ring.

The compound exhibits antibacterial properties and has high functionality such as acting as a layer transfer catalyst. Also,
The production method according to the present invention passes through four steps,
The compound represented by the above general formula (I) can be advantageously obtained industrially with high purity and high yield.

Next, the method for producing a pyridinium-type ionic optically active compound derivative having a basic structure of 1,3-dioxane ring represented by the above general formula (XI) to be provided by the present invention is described in the above-mentioned first method. The reaction is performed by the reactions in the first to fourth steps.

The first to third steps are carried out by the same reaction as in the method for producing the compound represented by the general formula (I), and the 4- (5-) represented by the aforementioned general formula (IV)
(Alkyl-1,3-dioxa-2-yl) pyridine compound (IV) is synthesized.

Next, in the fourth step, the following reaction formula (5)

[0088]

Embedded image (Wherein R ¹ , R ⁴ , and X have the same meanings as described above), and the 4- (5-alkyl-1,3-dioxa-2-yl) pyridine obtained in the third step is obtained. Compound (I
V) is reacted with an optically active alkyl halide represented by the formula: R ⁴ X to synthesize an optically active compound represented by the general formula (XI).

Specific examples of the optically active alkyl halide represented by R ⁴ X used in the reaction represented by the above reaction formula (5) include the following compounds. (S)-(+)-butyl chloride (S)-(+)-butyl bromide (S)-(-)-butyl chloride (S)-(-)-butyl bromide (S)-(+)-2- Methyl-1-butyl chloride (S)-(+)-2-methyl-1-butyl bromide (S)-(-)-2-methyl-1-butyl chloride (S)-(-)-2-methyl- 1-butyl bromide

(S)-(+)-5-methyl-1-heptyl chloride (S)-(+)-5-methyl-1-heptylbromide (S)-(−)-5-methyl-1-heptyl Chloride (S)-(-)-5-methyl-1-heptylbromide (S)-(+)-4-methyl-1-hexylbromide (S)-(+)-3-methyl-1-pentylbromide ( (S)-(+)-6-methyl-1-octyl bromide (S)-(+)-2-methyl-1-pentyl bromide (S)-(-)-2-methyl-1-pentyl bromide

The structural characteristic of the novel liquid crystalline compound represented by the general formula (XI) according to the present invention is that it is an optically active liquid crystalline compound and forms a pyridine ring connected to a 1,3-dioxane ring as a polar part. Having a positively charged nitrogen atom and two alkyl groups as a non-polar part.
Due to such a characteristic molecular structure, the optically active liquid crystalline compound of the present invention is a liquid crystal exhibiting a chiral smectic phase in which an optically active asymmetric carbon atom (chiral group) is introduced into a smectic liquid crystal molecule, and has ferroelectricity. For this reason, it has extremely excellent properties such as high-speed response, memory characteristics in which the alignment state of liquid crystal molecules is maintained even when voltage is removed, and bistability in which the orientation of molecules is in two stable states. have.

[0092]

EXAMPLES The present invention will now be described specifically with reference to examples, but it should not be construed that the invention is limited thereto.

Examples 1 and 2 First Step Diethyl-2-alkylmalonate was synthesized by the following reaction.

[0094]

Embedded image (Wherein, R represents C ₇ H ₁₅ or C ₁₀ H ₂₁ )

150 ml of ethanol is placed in a 500 ml Erlenmeyer flask, and after dissolving metallic sodium (0.3 mol), diethylmalonic acid (0.3 mol) is added. After cooling, alkyl bromide (0.3 mol) is added. Reflux in an ethylene glycol bath at 30 ° C. for 18 hours. After removing the solvent under reduced pressure, diethyl ether (300 ml) was added, and 300 ml of cold diluted hydrochloric acid (30 ml / 30 ml) was added using a separating funnel.
0 ml) followed by 100 ml of cold distilled water. After obtaining the ether layer, the aqueous layer is extracted again by adding 100 ml of diethyl ether. The diethyl ether solution obtained by liquid separation is dehydrated with anhydrous sodium sulfate for about 1 day. Filtered,
After removing diethyl ether under reduced pressure, the residue was distilled under reduced pressure to obtain compound (II ').

At this time, the two kinds of alkyl bromides (R
= C ₇ H ₁₅ , R = C ₁₀ H ₂₁ ) are shown in Table 1 below.

[0097]

[Table 1]

Second Step A 2-alkyl-1,3-propanediol was synthesized by the following reaction.

[0099]

Embedded image (Wherein, R represents C ₇ H ₁₅ or C ₁₀ H ₂₁ )

In a 500 ml three-necked round bottom flask, 100
ml of diethyl ether, lithium aluminum hydride (2 moles), and the compound (II ') (0.23 mol) obtained in the first step while cooling with ice.
l) is dissolved in 100 ml of diethyl ether and slowly added dropwise using a dropping funnel. Thereafter, the mixture is refluxed at 40 ° C. for 4 hours in an ethylene glycol bath. After the reaction, ethyl acetate (0.3 mol) is dissolved in 100 ml of diethyl ether under ice-cooling, and the mixture is slowly added dropwise using a dropping funnel. Then 50 ml of a saturated aqueous ammonium solution are slowly added dropwise with a dropping funnel. Thereafter, the flask is filled with diethyl ether and stirred at room temperature for 3 hours. Filtration and residue 300m
Dissolve in 1 liter of diethyl ether and stir for 24 hours. Add anhydrous sodium sulfate to the combined diethyl ether and add
After dehydration for a day, diethyl ether was removed under reduced pressure to obtain a compound (III ') as a residue. Table 2 shows the results.

[0101]

[Table 2]

Third Step By the following reaction, 4- (5-alkyl-1,3-dioxa-2-yl) pyridine was synthesized.

[0103]

Embedded image (Wherein, R represents C ₇ H ₁₅ or C ₁₀ H ₂₁ )

As a reaction device, a Dean-Stark-Trap was used.
In a 100 ml Erlenmeyer flask, the compound (III ') (0.03 mol) obtained in the second step was added to 60 ml of benzene, and the following experiment was performed for each.

That is, pyridine-4-aldehyde (equimolar number) is dissolved in each flask as described above, and 10 g of p-toluenesulfonic acid is added to adjust the pH to 1 or less. pH
After confirming that the mixture is refluxed in a silicone bath at 135 ° C to 140 ° C for 5 hours. After cooling, the residue is dissolved in diethyl ether (300 ml), washed with an aqueous solution of sodium carbonate (30 g / 300 ml) to confirm that the aqueous solution is basic, and then washed with distilled water (100 ml) to obtain a diethyl ether layer. Then, dehydrate with anhydrous sodium sulfate for about 1 day. After filtration, diethyl ether is removed under reduced pressure to obtain a residue. First, hexane 3 was obtained by column chromatography using silica gel.
The mixture was separated by flowing 00 ml and flowing 300 ml of benzene. The desired product eluted in the benzene solvent. After removing the solvent, the product was recrystallized 3 to 4 times with special grade hexane to obtain a compound (IV '). Table 3 shows the results.

[0106]

[Table 3]

Fourth Step N-alkyl-4- (5-alkyl-1,3-dioxa-2-yl) pyridinium bromide was synthesized by the following reaction.

[0108]

Embedded image (Wherein R is C ₇ H ₁₅ or C ₁₀ H ₂₁ , R ′ is C ₂ H ₅
R)

In a 200-ml three-necked round-bottomed flask, 0.0017 mol of each of the two compounds (IV ') obtained in the third step and 10-fold mol of ethyl bromide were dissolved in 30 ml of special-grade acetonitrile. At 100 ° C. for 24 hours in a silicone bath. Acetonitrile was removed under reduced pressure, reprecipitated with a mixed solution of 30 ml of hexane and 30 ml of diethyl ether, and washed by stirring for about one day.
After obtaining an insoluble matter, it was dried under vacuum to obtain a compound (I '). Table 4 shows the obtained results.

[0110]

[Table 4]

Examples 3 and 4 First to Third Steps Instead of RBr (R is C ₇ H ₁₅ ) as a starting material in Example 1, R ^a Br (R ^a is C ₉ H ₁₉ or C ₁₁ H) is used. ₂₃ is shown)
Were synthesized in the same manner as in the first to third steps of Example 1 using the two types of compounds, respectively, to obtain 4- (5-alkyl-1,3-dioxa-2 represented by the following formula: -Yl) pyridine compound (VII) was synthesized.

[0112]

Embedded image (Wherein ^Ra represents C ₉ H ₁₉ or C ₁₁ H ₂₃ ) Yield, yield, properties, m.p. of compound (VII) p. Table 5 shows the results.

[0113]

[Table 5]

Fourth Step N-alkyl-4- (5-alkyl-1,3-dioxa-2-yl) pyridinium bromide was synthesized by the following reaction.

[0115]

Embedded image (Where ^Ra is C ₉ H ₁₉ or C ₁₁ H ₂₃ , R ′ is C ₂ H
₅ indicates R)

In a 200-ml three-necked round-bottomed flask, 0.0017 mol of each of the two kinds of compounds (VII) obtained in the third step and 10-fold mol of ethyl bromide were dissolved in 30 ml of special-grade acetonitrile, and the mixture was dissolved under a nitrogen stream. Reflux at 100 ° C. for 24 hours in a silicone bath. Acetonitrile was removed under reduced pressure, reprecipitated with a mixed solution of 30 ml of hexane and 30 ml of diethyl ether, and washed by stirring for about one day.
After obtaining an insoluble matter, it was dried under vacuum to obtain a compound (I '). Table 6 shows the obtained results.

[0117]

[Table 6]

Next, ¹ H-NMR (CDC) of the compound represented by the general formula (I) obtained in Examples 1 to 4 was used.
l ₃ , δ) and FT-IR (CHCl ₃ , cm ^-1 ) are shown below.

(Example 1)

[0120]

Embedded image

¹ H-NMR (CDCl ₃ , δ); 0.8
5 to 1.83 (m, 19H, (a) + (g) +
(H)) 3.37-4.38 (m, 4H, (f)),
5.07 (q, 2H, J _ab = 6.70 Hz, (b)),
5.48 (s, 1H, (e)), 8.08 (d, 2H,
J _cd = 6.40 Hz, (c)), 9.75 (d, 2H,
J _cd = 6.40 Hz, (d)) FT-IR (CHCl ₃ , cm ⁻¹ );
0 (CH stretching vibration), 1650 (C = C, C = N stretching vibration), 1085 (COC stretching vibration), 890 (pyridine ring CH out-of-plane bending vibration)

(Example 2)

[0123]

Embedded image

¹ H-NMR (CDCl ₃ , δ); 0.8
7 to 1.85 (m, 25H, (a) + (g) +
(H)) 3.38-4.40 (m, 4H, (f)),
5.12 (q, 2H, J _ab = 6.70 Hz, (b)),
5.58 (s, 1H, (e)), 8.12 (d, 2H,
J _cd = 6.40 Hz, (c)), 9.78 (d, 2H,
J _cd = 6.40 Hz, (d)) FT-IR (CHCl ₃ , cm ⁻¹ );
0 (CH stretching vibration), 1655 (C = C, C = N stretching vibration), 1095 (COC stretching vibration), 890 (pyridine ring CH out-of-plane bending vibration)

(Embodiment 3)

[0126]

Embedded image

[0127] ¹ H-NMR (CDCl ₃ , δ);
0.91 to 1.89 (m, 23H, (a) + (g) +
(H)) 3.48 to 4.53 (m, 4H, (f)),
5.24 (q, 2H, J_ab= 6.70 Hz,
(B)) 5.53 (s, 1H, (e)), 8.33
(D, 2H, J_cd= 6.40 Hz, (c)), 9.9
4 (d, 2H, J_cd= 6.40 Hz, (d))FT-IR (CHCl ₃ , cm ⁻¹ ); 2950, 2
875 (CH stretching vibration), 1660 (C = C, C = N
Stretching vibration), 1100 (CO-C stretching vibration), 900
(Pyridine ring CH out-of-plane bending vibration)

(Example 4)

[0129]

Embedded image

¹ H-NMR (CDCl ₃ , δ); 0.9
6 to 1.93 (m, 27H, (a) + (g) +
(H)) 3.47-4.49 (m, 4H, (f)),
5.22 (q, 2H, J _ab = 6.70 Hz, (b)),
5.72 (s, 1H, (e)), 8.28 (d, 2H,
J _cd = 6.40 Hz, (c)), 9.91 (d, 2H,
J _cd = 6.40 Hz, (d)) FT-IR (CHCl ₃ , cm ⁻¹ );
0 (CH stretching vibration), 1642 (C = C, C = N stretching vibration), 1080 (COC stretching vibration), 880 (pyridine ring CH out-of-plane bending vibration)

Next, the results of measurement of the phase transition temperatures of the compounds represented by the general formula (I) obtained in Examples 1 to 4 are shown in Table 7 below.

[0132]

[Table 7]

In Table 7, R = n-C ₇ H of Example 1
The compound No. ₁₅ does not show a smectic A liquid crystal phase, because the alkyl group needs to be longer than a certain length in order to show a smectic liquid crystal phase. However, when this compound is used as a mixture in a mixed liquid crystal system, even if the compound does not have a liquid crystal phase alone, if the molecule has the same shape, the mixed system can show a smectic liquid crystal phase. It can be used as a material.

Example 5 First Step to Third Step In the same manner as in Example 2, a 4- (5-decyl-1,3-dioxa-2-yl) pyridine compound was synthesized.

Fourth step 0.46 g (1.51 mmol) of 4- (5-decyl-1,3-dioxa-2-yl) pyridine obtained in the third step was added to 100 ml of brown ampoulebin. S)-(+)
A solution prepared by dissolving 2.27 g (15 mmol) of -1-promo-2-methylbutane in 30 ml of special grade acetonitrile was charged, and vacuum and nitrogen substitution were repeated three times according to a conventional method to expel air, and then sealed. The mixture was heated and reacted in a constant temperature oven at 60 ° C. for 3 days. The ampoule was opened after cooling, and acetonitrile was removed under reduced pressure.
The precipitate was reprecipitated with a mixed solution of 30 ml of diethyl ether to about 1
After washing by stirring for one day to obtain an insoluble material, the product was dried under vacuum to a melting point of 51%.
0.69 g of a white crystal at a temperature of ° C was obtained. As a result of analysis, the product was found to be N- (S)-(+)-2-methylbutyl-4- (5
-Decyl-1,3-dioxa-2-yl) pyridium bromide and the yield was 100%.

[0136]

Embedded image

¹ H-NMR (CDCl ₃ , δ); 0.8
1-1.74 (m, 31H, (a) + (g) +
(H)) 3.43 to 4.44 (m, 4H, (f)),
4.94 (q, 2H, J _ab = 6.70 Hz,
(B)) 5.66 (s, 1H, (e)), 8.19
(D, 2H, J _cd = 6.40 Hz, (c)), 9.6
9 (d, 2H, J _cd = 6.40 Hz, (d)) FT-IR (CHCl ₃ , cm ⁻¹ );
50 (CH stretching vibration), 2250 (pyridium), 1
648 (C = C, C = N stretching vibration), 1090 (C-O
-C stretching vibration), 880 (pyridine ring CH out-of-plane bending vibration)

Example 6 First Step to Third Step The first to third steps of Example 1 were repeated using C ₁₈ H ₃₇ Br in place of RBr (R is C ₇ H ₁₅ ) as the starting material of Example 1. By performing the same method as in the third step, a 4- (5-octadecyl-1,3-dioxa-2-yl) pyridine compound was synthesized. The yield was 4.6 g, the yield was 65%, the properties were white crystals, and the melting point was 88 ° C.

Fourth Step N- (S)-(+)-2-Methylbutyl-4- (5-octadecyl-1,3-dioxa-2-yl) pyridium bromide was synthesized in the same manner as in Example 5. did. The yield was 0.86 g, the yield was 100%, the properties were white crystals, and the melting point was 65 ° C.

[0140]

Embedded image

¹ H-NMR (CDCl ₃ , δ); 0.8
8 to 1.79 (m, 47H, (a) + (g) +
(H)) 3.43 to 4.45 (m, 4H, (f)),
4.95 (q, 2H, J _ab = 6.70 Hz,
(B)) 5.64 (s, 1H, (e)), 8.17
(D, 2H, J _cd = 6.40 Hz, (c)), 9.5
5 (d, 2H, J _cd = 6.40 Hz, (d)) FT-IR (CHCl ₃ , cm ⁻¹ );
70 (CH stretching vibration), 2280 (pyridium), 1
658 (C = C, C = N stretching vibration), 1110 (C-O
-C stretching vibration), 895 (pyridine ring CH out-of-plane bending vibration)

Next, the results of measurement of the phase transition temperatures of the compounds represented by the general formula (XI) obtained in Examples 5 and 6 are shown in Table 8 below.

[0143]

[Table 8]

In Table 8, Examples 5 and 6 are examples in which an optically active asymmetric carbon atom (chiral group) is introduced into the smectic liquid crystal molecules, and can exhibit a chiral smectic liquid crystal phase and can be used as a liquid crystal material. It is.

[0145]

As described above, according to the present invention, a novel pyridinium-type ionic compound derivative can be provided, and this compound is expected to be useful as a thermotropic liquid crystal substance exhibiting smectic A phase liquid crystallinity. is there.

Further, according to the present invention, a novel pyridinium-type ionic optically active compound derivative can be provided, and this compound is a thermotropic liquid crystal material exhibiting a liquid crystallinity of a chiral smectic phase in which an optically active chiral group is introduced into a smectic liquid crystal molecule. Has ferroelectricity and can be expected to be useful. Further, according to the production method of the present invention, the pyridinium-type ionic compound derivative and the pyridinium-type ionic optically active compound derivative can be industrially advantageously obtained.

Claims (7)

[Claims] 1. A compound represented by the following general formula (I): Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 22 carbon atoms, and X is a halogen atom. A pyridinium-type ionic compound derivative having a basic structure of a 1,3-dioxane ring . 2. In the general formula (1), R ¹ has 9 carbon atoms.
To 11 alkyl group, R ² represents an ethyl group, X is pyridinium ion compound derivative of claim 1 wherein the bromine atom. 3. The method for producing a pyridinium-type ionic compound derivative having a basic structure of 1,3-dioxane ring according to claim 1, comprising the following first step to fourth step. (A) a compound represented by the formula: R ¹ X (wherein R ¹ and X are as defined above), and a compound represented by the formula: (Wherein, R ³ represents a lower alkyl group having 1 to ³ carbon atoms), and reacted with a compound represented by the general formula (II): (Wherein R ¹ and R ³ are as defined above), (b) reducing the compound represented by the general formula (II) obtained in the first step, And the general formula (III) (Wherein, R ¹ has the same meaning as described above), (c) a compound represented by the general formula (III) obtained in the second step, and pyridine-4-aldehyde Is reacted with a compound represented by the general formula (IV): (Wherein R ¹ has the same meaning as described above), (d) a compound represented by the general formula (IV) obtained in the third step, and a compound represented by the formula: R ² X (Where
R ² and X have the same meanings as defined above), and are reacted with a compound represented by the general formula (I). (Wherein R ¹ and R ² have the same meanings as described above) in the fourth step of synthesizing a pyridinium-type ionic compound derivative having a basic structure of 1,3-dioxane ring. 4. A liquid crystal material comprising the pyridinium-type ionic compound derivative according to claim 1 as an active ingredient. 5. The following general formula (XI): (Wherein, R ¹ represents the same or different alkyl group having 1 to 22 carbon atoms, X represents a halogen atom, and R ⁴ represents the following formula (X
Represents an optically active group represented by II). Embedded image Here, Y represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 10, n represents an integer of 1 to 9, and * represents an asymmetric carbon atom. A) a pyridinium-type ionic optically active compound derivative having a basic structure of an l, 3-dioxane ring; 6. The method for producing a pyridinium-type ionic optically active compound derivative having a basic structure of an 1,3-dioxane ring according to claim 5, comprising the following first to fourth steps. (A) a compound represented by the formula: R ¹ X (wherein R ¹ and X are as defined above), and a compound represented by the formula: (Wherein R ³ represents a lower alkyl group having 1 to ³ carbon atoms), and reacted with a compound represented by the general formula (II): (Wherein R ¹ and R ³ are as defined above), (b) reducing the compound represented by the general formula (II) obtained in the first step, And the general formula (III) (Wherein, R ¹ has the same meaning as described above), (c) a compound represented by the general formula (III) obtained in the second step, and pyridine-4-aldehyde Is reacted with a compound represented by the general formula (IV): (Wherein R ¹ is as defined above), (d ') a compound represented by the general formula (IV) obtained in the third step, and a compound represented by the formula: R ⁴ X (where
R ⁴ and X have the same meanings as defined above), and are reacted with a compound represented by the general formula (XI). (Wherein, R ¹ and R ⁴ are as defined above)
A fourth step of synthesizing a pyridinium-type ionic optically active compound derivative having a basic structure of a 3-dioxane ring. 7. A liquid crystal material comprising the pyridinium-type ionic optically active compound derivative according to claim 5 as an active ingredient.