JP2012188389A - Compound having stable radical structure, and sol, gel and xerogel made using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable radical-containing compound having functions as a surfactant to organize a stable radical compound, and to provide a micelle and an emulsion made using the compound.SOLUTION: There are provided a compound having in a molecule a stable radical structure and a part having hydrogen bonding ability and also a sol, a gel and a xerogel containing the compound. As the xerogel containing a stable radical has a three-dimensional network structure, so it has a high radical density per unit surface area and is usable for an electrode material of an organic radical cell and the like.

Description

  The present invention relates to a compound having a stable radical structure and a sol, gel or xerogel having a stable radical.

  In recent years, liquid crystal materials having a stable radical structure have been found, and application to mass transport by magnetic field control has been studied (Patent Documents 1 and 2). It has also been found that polymer materials containing stable radicals have excellent properties as electrode materials for organic radical batteries (Patent Document 3). On the other hand, gelling agents are widely used and have a wide range of applications.

  By the way, in order to utilize the function of a stable radical, it is important to organize and increase the density of the radical structure. So far, it has been used as an electrode material as a polymer having a stable radical structure. Higher density is required for high-performance radical materials.

  As an example of a method for organizing a stable radical compound, there is a liquid crystal material having the above-described stable radical structure. However, even if a stable radical-containing liquid crystal is used, a gel or a xerogel having a three-dimensional network structure cannot be constructed.

JP 2009-215187 A JP 2009-79020 A Japanese Patent No. 3687736

  An object of the present invention is to provide a stable radical-containing compound having a function as a gelling agent in order to organize a stable radical compound, and to provide a xerogel having a sol, gel or three-dimensional network structure using the compound. There is to do.

  The present inventors have studied the addition of various functional groups to compounds containing stable radicals, and formed sols, gels, and xerogels containing stable radicals by imparting hydrogen bonding ability to compounds containing stable radicals. As a result, the present invention has been completed.

  The present invention provides a compound having a site having a stable radical structure and a hydrogen bonding ability in one molecule, and also provides a sol, gel or xerogel containing the compound and water or an organic solvent.

  In general, radical compounds are unstable and quickly disappear due to a chemical reaction in a general environment such as in the air. Therefore, it is difficult to use a normal radical compound as a material used for various purposes. On the other hand, since nitroxide radical compounds and the like are stable in air, they can be used for materials reflecting special properties as radicals. For example, organized radical materials can develop paramagnetism, ferromagnetism, and the like. By incorporating a stable radical into a compound exhibiting liquid crystallinity, an organized radical structure can be constructed, which can be moved using a magnetic field such as a magnet.

  On the other hand, a gelling agent can form a sol, gel or xerogel by mixing with water or an organic solvent. A sol is a colloid of a liquid dispersion system. A colloid is a substance state composed of two pairs of phases, one of which forms fine droplets or fine particles (dispersed phase) and the other is dispersed. A gel is essentially the same as a sol, but has a high viscosity due to a dispersoid network, loses fluidity, and becomes a solid as a whole system. The dried gel is xerogel. In general, xerogel has a three-dimensional network structure and a large surface area. For example, silica gel is a typical xerogel and has high hygroscopicity. The gelling agent is required to have the ability to build a certain type of tissue structure or network structure in water or an organic solvent system, and it is important to have a site such as a hydrogen bond in the molecule. That is, molecules aggregate in the system due to intermolecular hydrogen bonding, and at that time, some kind of organization is performed by intermolecular interaction of the whole molecule. Depending on the aggregation level, a sol or gel is formed.

  Since the compound having a stable radical structure of the present invention has a function as a gelling agent, sols, gels, and xerogels having a stable radical structure can be easily produced. In particular, xerogel having a stable radical structure has a large surface area because it has a three-dimensional network structure, and can be applied to various materials utilizing stable radicals. Moreover, since the xerogel containing a stable radical has a three-dimensional network structure, it has a high radical density per unit surface area and can be used for an electrode material such as an organic radical battery.

It is an ESI-MS spectrum of (S, S, S) -1. 1 is a ¹ H NMR spectrum of (S, S, S) -1. It is a ¹³ C NMR spectrum of (S, S, S) -1. This is a hydrogel using (S, S, S) -1. It is a figure showing the DSC analysis result of hydrogel (S, S, S) -1. Polarization microscope images of (S, S, S) -1 hydrogel: 200 × (left) and 1000 × (right). SEM images of xerogel of (S, S, S) -1: 500 times (left) and 10000 times (right). It is a figure showing the temperature dependence of the EPR spectrum of the hydrogel of (S, S, S) -1. It is a figure showing the temperature dependence (right) of the line width ((DELTA) H) (left) and g value of the hydrogel of (S, S, S) -1.

  The present invention relates to a compound having a stable radical structure and hydrogen bonding ability in one molecule, and this radical compound is characterized in that a three-dimensional structure is constructed in water or in an organic solvent.

  Specifically, the compound of the present invention is preferably a compound represented by the following general formula (A1).

(Wherein, W represents the structure of any one of the following general formulas (W-1) to (W-3),
(In the formula, Ra and Rb each independently represent a hydrogen atom or an alkyl having 1 to 12 carbon atoms.)
In the formula, R is hydrogen or an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, or an alkenyloxy group having 2 to 30 carbon atoms (1 in each group). One or more hydrogen atoms may be independently substituted with fluorine atoms, and one or two or more of —CH ₂ — in each group are independent of each other and oxygen atoms are not directly bonded to each other. -O-, -S-, -CO-, -COO-, -OCO-, -OCS-, -SCO-, -CONR ^0- , -NR ⁰ CO- (wherein R ⁰ is a hydrogen atom or Represents an alkyl group having 1 to 12 carbon atoms.), —CH═N—, —N═CH—, —N═N— or —CH═CH—may be substituted), or P—Sp—. Represents
(In the formula, P represents any structure of the following formulas (R-1) to (R-15),
Sp represents a C2-C12 alkylene group in which carbon atoms may be replaced by oxygen atoms, -COO-, -OCO-, or -OCOO-, or a single bond, assuming that oxygen atoms are not directly bonded to each other. )
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group (one or more hydrogen atoms in each group are independently Optionally substituted with a fluorine atom or a chlorine atom, and one or more CHs of the aromatic ring in the group may be independently substituted with N.), or represents a single bond,
m and n each independently represent 0, 1, 2, or 3, m + n is an integer from 1 to 6;
Z ¹ and Z ² are each independently —O—, —S—, —CO—, —COO—, —OCO—, —OCS—, —SCO—, —CONR ¹ —, —NR ¹ CO—, — _{CH 2 -, - OCH 2 -} , - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 -, - OCF 2 -, - CF 2 O -, - CF 2 CH 2 -, - CH ₂ CF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CH—, or a single bond,
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
V represents a C2-C12 alkylene group in which a carbon atom may be replaced by an oxygen atom, -COO-, -OCO-, or -OCOO-, or a single bond, assuming that oxygen atoms are not directly bonded to each other;
X is - represents _{^{(CONY 1 -CHY 2) j -R}} 2,
Wherein Y ¹ represents (Z ³ -A ³ ) _k -R ³ , Y ² represents (Z ⁴ -A ⁴ ) ₁ -R ⁴ ,
(Wherein A ³ and A ⁴ are independently of each other a trans-1,4-cyclohexylene group or 1,4-phenylene group, naphthalene-2,6-diyl group, indole-3,6-diyl group, pyrrolidine. -2,4-diyl group, imidazole-4,5-diyl group (one or more hydrogen atoms in each group may be independently substituted with fluorine atoms or chlorine atoms, One or more CH in the ring may be independently substituted with N.) or represents a single bond,
Z ³ and Z ⁴ are each independently —O—, —S—, —CO—, —COO—, —OCO—, —OCS—, —SCO—, —CONR ⁵ —, —NR ⁵ CO—, — _{CH 2 -, - OCH 2 -} , - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 -, - OCF 2 -, - CF 2 O -, - CF 2 CH 2 -, - CH ₂ CF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CH—, or a single bond, R ³ , R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
j, k and l each independently represents 0, 1, 2 or 3. )
R ² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms (one in each group) The above hydrogen atoms may be independently substituted with fluorine atoms, and one or two or more —CH ₂ — in each group may be independently independent of each other and oxygen atoms are not directly bonded to each other. , -O-, -S-, -CO-, -COO-, -OCO-, -OCS-, -SCO-, -CONR ^0- , -NR ⁰ CO-, -CH = N-, -N = CH -, -N = N-, -CH = CH-, or may be substituted with a single bond). )

  W, which is a stable radical structure, is preferably (W-1) when importance is attached to the linearity of the molecule. In this case, the substituted alkyl groups Ra and Rb are preferably a methyl group or an ethyl group.

R is preferably an alkoxy group having 10 to 20 carbon atoms, an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, more preferably an alkoxyl having 10 to 20 carbon atoms or an alkyl group having 10 to 20 carbon atoms. An alkoxyl group having 10 to 20 carbon atoms is particularly preferable. In the case where R represents "P-Sp-", the P is preferably the formula (R-1) or the formula (R-2) from the viewpoint of ease of polymerization, and the Sp is a terminal -CH _2-. An alkylene group having 3 to 8 carbon atoms which may be substituted with -O- is preferable.

A ¹ and A ² are each independently preferably a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a naphthalene-2,6-diyl group, and a 1,4-phenylene group or a trans-1, A 4-cyclohexylene group is more preferable, and a 1,4-phenylene group is particularly preferable.

Z ¹ is preferably a single bond, —COO — (— C (═O) —O—) or —OCO — (— O—C (═O) —), more preferably a single bond or —COO—. Bonding is particularly preferred.
Z ² is preferably a single bond, —OCO— or —COO—, more preferably a single bond or —OCO—, and particularly preferably a single bond.

m and n are each independently preferably 1, 2 or 3, more preferably 1 or 2. At this time, m + n is preferably 2, 3, 4 or 5, and more preferably 2, 3 or 4.
When m or n is 2 to 3, a plurality of Z ¹ , A ¹ , Z ² and A ² in the formula (A1) are independent of each other.

R ⁰ and R ¹ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
When a plurality of R ⁰ or R ¹ are contained in the formula (A1), the plurality of R ⁰ and R ¹ are independent from each other.

  V is preferably an alkylene group having 2 to 6 carbon atoms or a single bond in which the carbon atom may be replaced by an oxygen atom, -COO-, -OCO- or -OCOO-, assuming that the oxygen atoms are not directly bonded to each other. Bonding is more preferred.

Suitable X, for example, - (CONH-CHCH ₃₎ represented by formula with _j -R ² (X-01) are mentioned. In formula (X-01), k is 0, l is 0, R ³ is a hydrogen atom, and R ⁴ is a methyl group, whereby Y ¹ is a hydrogen atom and Y ² is a methyl group. It is a thing.
In formula (X-01), j is preferably 1 or 2.

R ² is one in which one or two or more —CH ₂ — are independent of each other and oxygen atoms are not directly bonded to each other, and —O—, —S—, —CO—, —COO—, —OCO— , -OCS-, -SCO-, -CONR ^0- , -NR ⁰ CO-, -CH = N-, -N = CH-, -N = N-, or -CH = CH- A good methyl group or ethyl group, or a hydrogen atom is preferable, and one or two or more —CH ₂ — are independent of each other and oxygen atoms are not directly bonded to each other, —O—, —S—, —CO -, - COO -, - OCO -, - OCS -, - SCO -, - CONR 0 -, - NR 0 CO -, - CH = N -, - N = CH -, - N = N-, or -CH A methyl group or ethyl group which may be substituted with ═CH— is more preferable.

In the present invention, among the monovalent hydrocarbon groups constituting R and R ² , —CH ₂ — may be substituted as described above. At this time, since —CH _{3 at} the end of the monovalent hydrocarbon is —CH ₂ —H, it can be similarly substituted. For example, —CH ₂ — in —CH _{3 at} the end of R ₂ can be substituted with —COO— to become —COOH.

When emphasizing amphiphilicity, A ¹ and A ² are each independently preferably a trans-1,4-cyclohexylene group or 1,4-phenylene group, and m and n are each independently preferably 1 to 2. , Z ¹ and Z ² are each independently preferably —COO— or a single bond. Further, j is preferably 1 when a relatively weak hydrogen bonding ability is required, but j is preferably 2 or 3 when a higher hydrogen bonding ability is required.

  The general formula (A1) preferably has a structure represented by the following general formula (A2).

(In the formula, R, A ¹ , A ² , m, n, Z ¹ , Z ² , V and X represent the same meaning as in the general formula (A2).)

The general formula (A2) includes various compounds depending on combinations of R, A ¹ , A ² , m, n, Z ¹ , Z ² , V, and X. Specifically, the compounds shown below Is preferred.

(In the formula, Ra and Rb each independently represent an alkyl group having 1 to 2 carbon atoms, and Rc represents an alkyl group having 12 to 18 carbon atoms, an alkenyl group having 12 to 18 carbon atoms, or 12 to 18 carbon atoms. Represents an alkoxyl group or an alkenyloxy group having 12 to 18 carbon atoms.)

Of the above-mentioned compounds, the compounds represented by the general formulas (Ia-1) to (Ia-3) are preferable when the radical density is to be increased, and when the lipophilicity is to be increased, the general formula (I- b-1) to (Ib-3), (Ic-1) to (Ic-3), or (Id-1) to (Id-3) preferable.
On the other hand, when it is desired to enhance the hydrogen bonding ability, compounds represented by the general formulas (II-a-1) to (II-a-3) are preferable. Furthermore, when it is desired to perform polymerization after forming a sol or xerogel, compounds represented by general formulas (III-a-1) to (III-a-3) are preferable.

In the general formula (A2), R represents an alkyl group having 10 to 20 carbon atoms or an alkoxyl group having 10 to 20 carbon atoms, A ¹ represents a 1,4-phenylene group, and A ² represents a 1,4-phenylene group. M, n are each independently 1 or 2, and Z ¹ and Z ² are each independently —COO—, —OCO— or a single bond.

  Since the compound of the present invention has a stable radical structure, it can exhibit paramagnetism or ferromagnetism, and can be used as a functional organic material capable of controlling movement by a magnetic field. Further, since the radical structure can be organized and densified, it can be suitably used as an electrode material or the like as a polymer having a stable radical structure.

  When the compound of the present invention is used as a gelling agent, it may be composed of only one kind of the compound of the present invention or may be composed of two or more kinds. These additives may be added.

  The compound of the present invention is a gelling agent that controls fluidity of adhesives, paints, printing inks, cosmetics, etc., imparts thixotropy, prevents the diffusion of mineral oil at sea, solidifies disposal of edible oil, food manufacturing industry, medical It can be used in fields.

  The compound of the present invention is used as a gelling agent, and it is necessary to use water or an organic solvent in order to form a sol, gel, or xerogel.

  That is, the sol according to the present invention contains the aforementioned compound of the present invention and water or an organic solvent. Moreover, the gel concerning this invention contains the compound of this invention mentioned above, water, or an organic solvent. The xerogel according to the present invention is produced by drying the gel.

  Examples of the aqueous solvent for use in the present invention include water, a water-soluble organic solvent, or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol and t-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, Aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and N-methylpyrrolidone; glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; glycol solvents such as ethylene glycol and propylene glycol; Ether solvents such as diethyl ether, tetrahydrofuran and dioxane can be used.

Example 1 Synthesis of Carboxylic Acid Proxy 3

Magnesium (243 mg, 10 mmol) was heated and vacuum dried for 1 hour. P-Bromobenzaldehyde diethyl acetal (2.591 g, 10 mmol) was dissolved in THF and added to magnesium. Further, a small amount of iodine was added, heated and stirred for 4 hours to obtain a Grignard reagent. Well-dried nitrone (565 mg, 5 mmol) was dissolved in THF (10 mL), added to the previous Grignard reagent at −78 ° C., and stirred overnight. Saturated aqueous ammonium chloride solution (50 mL) was added to the reaction mixture, and the mixture was extracted with dichloromethane (50 mL × 2). After drying over anhydrous MgSO ₄ , the solvent is removed, the residue is dissolved in methanol (20 mL), 25% concentrated aqueous ammonia (2 mL) and Cu (OAc) ₂ · H ₂ O (160 mg) are added, and oxygen is injected for 2 minutes. did. After the solution turned dark blue, the solvent was removed, saturated aqueous sodium hydrogen carbonate solution (50 mL) was added, and the mixture was extracted with chloroform (50 mL × 2). The solvent was removed after drying over anhydrous MgSO ₄ .
Magnesium (243 mg, 10 mmol) was heated and vacuum dried for 1 hour. Alkyl bromide (3.682 g, 10 mmol) was dissolved in THF (10 mL) and added to magnesium. Further, a small amount of 1,2-dibromoethane was added, heated and stirred for 4 hours to obtain a Grignard reagent. The previous residue was dissolved in THF, added to this Grignard reagent at -78 ° C, and stirred overnight. Saturated aqueous ammonium chloride solution (50 mL) was added to the reaction mixture, and the mixture was extracted with dichloromethane (50 mL × 2). After drying over anhydrous MgSO ₄ , the solvent is removed, the residue is dissolved in methanol (20 mL), 25% concentrated aqueous ammonia (2 mL) and Cu (OAc) ₂ · H ₂ O (160 mg) are added, and oxygen is injected for 2 minutes. did. After the solution turned dark blue, the solvent was removed, saturated aqueous sodium hydrogen carbonate solution (50 mL) was added, and the mixture was extracted with chloroform (50 mL × 2). The solvent was removed after drying over anhydrous MgSO ₄ . The product was purified by silica gel column chromatography (hexane-ether: v / v 90:10).
Since the obtained diarylproxyl was a diethyl acetal protector, it was dissolved in THF (5 mL), and 3 mL of dilute sulfuric acid (5%) was added for deprotection. Saturated aqueous sodium chloride solution (50 mL) was added, and the mixture was extracted with dichloromethane (50 mL × 2). The solvent was removed after drying over anhydrous MgSO ₄ .
A residue dissolved in THF (2 mL) in 1 mL of Ag ₂ O (89 mg, 0.40 mmol) and aqueous sodium hydroxide (10%) was added, and the mixture was stirred at 60 ° C. for 1 hour. Purification by silica gel column chromatography (hexane-ether: v / v 50:50) gave carboxylic acid proxyl 3 (total yield: 6%).

Example 2 Synthesis of (S, S, S) -1

  Carboxylic acid 3 (30mg, 0.114mmol) dissolved in DMF (500μL) and HOBt (1-hydroxybenzotriazole) (5mg, 1.1eq) and EDC (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide) (6mg, 1.1eq ) Was added and stirred at room temperature for 1 hour. Alanine (20 mg, 2 eq) and potassium carbonate (4 mg, 1 eq) dissolved in water (100 μL) were added and stirred for 2 hours. Water (10 mL) and dichloromethane (10 mL) were added to bring the pH of the aqueous phase to 3, and the organic phase was separated. Purification by silica gel column chromatography (chloroform-methanol: v / v 95: 5) gave (S, S, S) -1 (yield 48%).

The ESI-MS spectrum of (S, S, S) -1 is shown in FIG. Further, a ¹ H NMR spectrum of (S, S, S) -1 for structure identification is shown in FIG. 2, and a ¹³ C NMR spectrum of (S, S, S) -1 is shown in FIG.

¹ H NMR (after reduction with 500 MHz, CDCl ₃ , hydrazobenzene) δ 0.88 (s, 3H), 1.26 (s, 24H), 1.49-1.87 (m, 12H), 3.48 (dd, J = 6.5, 3H), 3.98 (s, 1H), 6.82-87 (m, 4H + 6H (hydrazobenzene)), 7.48-7.54 (m, 4H + 6H (azobenzene))
¹³ C NMR (after reduction with 500 MHz, CDCl ₃ , hydrazobenzene) δ 14.3, 22.8, 25.9, 26.0, 26.2, 28.3, 29.5, 29.6, 29.7, 29.8, 31.9, 32.0, 32.4, 34.5, 36.8, 63.2, 68.1, 68.8 , 69.3, 112.8, 113.2, 114.0, 122.9, 127.1, 128.1, 129.5, 134.6, 137.8, 156.5, 157.9 192.3
IR (KBr) ν 3446, 2976, 2922, 2852, 2372, 2345, 1719, 1560, 1462, 1290, 1250, 897, 831, 774 cm ^-1
Hydrazobenzene: ¹ H NMR (500MHz, CDCl ₃ ) δ 5.63 (s, 2H), 6.82-6.87 (m, 6H), 7.21 (t, J = 8.0, 4H): ¹³ C NMR (500MHz, CDCl ₃ ) δ 112.4 , 120.0,129.2, 149.0
Azobenzene: ¹ H NMR (500MHz, CDCl ₃ ) δ 7.48-54 (m, 6H), 7.93 (d, J = 8.5Hz, 4H): ¹³ C NMR (500MHz, CDCl ₃ ) δ 123.0, 129.2, 129.7, 152.8

(Example 3) Preparation of gel The gelling agent (S, S, S) -1 was dissolved in water by heating and cooled to room temperature to form a hydrogel (FIG. 4). This hydrogel was a thermoreversible hydrogel that repeatedly transformed into a sol when heated and a gel when cooled. As a result of DSC measurement, it was found that the gel-sol transition temperature was 60 ° C. (FIG. 5). Further, by observation with a polarizing microscope, birefringence disappeared at 60 ° C., and gel-sol transition was confirmed (FIG. 6). A characteristic three-dimensional network structure was confirmed by SEM observation of xerogel (FIG. 7). When the temperature dependence of the EPR spectrum of the hydrogel was measured, it was found that the line width (ΔH) and g value changed greatly at 60 ° C. (FIGS. 8 and 9).

(Comparative Example 1)
No gel was formed when the following stable radical liquid crystal material was mixed with water at any ratio.

(Comparative Example 2)
No gel was formed when the following stable radical liquid crystal material was mixed with water at any ratio.

Claims (7)

A compound having a site having a stable radical structure and hydrogen bonding ability in one molecule. The compound of Claim 1 represented by general formula (A1).
(Wherein, W represents the structure of any one of the following general formulas (W-1) to (W-3),
(In the formula, Ra and Rb each independently represent a hydrogen atom or an alkyl having 1 to 12 carbon atoms.)
R is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, or an alkenyloxy group having 2 to 30 carbon atoms (one or more in each group) In which each hydrogen atom may be independently substituted with a fluorine atom, and one or two or more —CH ₂ — in each group are independently of each other, and oxygen atoms are not directly bonded to each other. —O—, —S—, —CO—, —COO—, —OCO—, —OCS—, —SCO—, —CONR ⁰ —, —NR ⁰ CO— (wherein R ⁰ is a hydrogen atom or a carbon number) Represents an alkyl group of 1 to 12.), -CH = N-, -N = CH-, -N = N- or -CH = CH- may be substituted)), or P-Sp-. ,
(In the formula, P represents any structure of the following formulas (R-1) to (R-15),
Sp represents a C2-C12 alkylene group in which carbon atoms may be replaced by oxygen atoms, -COO-, -OCO-, or -OCOO-, or a single bond, assuming that oxygen atoms are not directly bonded to each other. )
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group (one or more hydrogen atoms in each group are independently Optionally substituted with a fluorine atom or a chlorine atom, and one or more CHs of the aromatic ring in the group may be independently substituted with N.), or represents a single bond,
m and n each independently represent 0, 1, 2, or 3, m + n is an integer from 1 to 6;
Z ¹ and Z ² are each independently —O—, —S—, —CO—, —COO—, —OCO—, —OCS—, —SCO—, —CONR ¹ —, —NR ¹ CO—, — _{CH 2 -, - OCH 2 -} , - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 -, - OCF 2 -, - CF 2 O -, - CF 2 CH 2 -, - CH ₂ CF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CH—, or a single bond,
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
V represents a C2-C12 alkylene group in which a carbon atom may be replaced by an oxygen atom, -COO-, -OCO-, or -OCOO-, or a single bond, assuming that oxygen atoms are not directly bonded to each other;
X is - represents _{^{(CONY 1 -CHY 2) j -R}} 2,
Wherein Y ¹ represents (Z ³ -A ³ ) _k -R ³ , Y ² represents (Z ⁴ -A ⁴ ) ₁ -R ⁴ ,
(Wherein A ³ and A ⁴ are independently of each other a trans-1,4-cyclohexylene group or 1,4-phenylene group, naphthalene-2,6-diyl group, indole-3,6-diyl group, pyrrolidine. -2,4-diyl group, imidazole-4,5-diyl group (one or more hydrogen atoms in each group may be independently substituted with fluorine atoms or chlorine atoms, One or more CH in the ring may be independently substituted with N.) or represents a single bond,
Z ³ and Z ⁴ are each independently —O—, —S—, —CO—, —COO—, —OCO—, —OCS—, —SCO—, —CONR ⁵ —, —NR ⁵ CO—, — _{CH 2 -, - OCH 2 -} , - CH 2 O -, - SCH 2 -, - CH 2 S -, - CF 2 -, - OCF 2 -, - CF 2 O -, - CF 2 CH 2 -, - CH ₂ CF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CH—, or a single bond, R ³ , R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
j, k and l each independently represents 0, 1, 2 or 3. )
R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms (one in each group) The above hydrogen atoms may be independently substituted with fluorine atoms, and one or two or more —CH ₂ — in each group may be independently independent of each other and oxygen atoms are not directly bonded to each other. , -O-, -S-, -CO-, -COO-, -OCO-, -OCS-, -SCO-, -CONR ^0- , -NR ⁰ CO-, -CH = N-, -N = CH -, -N = N-, -CH = CH-, or may be substituted with a single bond). The compound of Claim 2 represented by general formula (A2).
(In the formula, R, A ¹ , A ² , m, n, Z ¹ , Z ² , V and X represent the same meaning as in the general formula (A1).) R is an alkyl group having 10 to 20 carbon atoms or an alkoxyl group having 10 to 20 carbon atoms, A ¹ is a 1,4-phenylene group, A ² is a 1,4-phenylene group, and m and n are each independently The compound according to claim 3, wherein Z ¹ and Z ² each independently represent —COO—, —OCO—, or a single bond. A sol containing the compound according to any one of claims 1 to 4 and water or an organic solvent. The gel containing the compound as described in any one of Claims 1-4, water, or an organic solvent. A xerogel prepared by drying the gel according to claim 6.