JP2863883B2 - Calixarene derivatives exhibiting flow birefringence - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calixarene derivative, and more particularly to a novel calixarene derivative having a low melting point and a flowable birefringent phase.

[0002]

2. Description of the Related Art Calixarenes are cyclic oligomers formed by the condensation reaction of phenol and formaldehyde, and have the molecular structure similar to that of the Greek holy grail (Calix). Was attached. Calixarenes were found in phenol-formaldehyde resins by Zinke et al. Around 1950 (A. Zinke, E. Zegler, Chem. Ber., 77,
264, (1944)) and later in the late 1970s, Kaemm
A cyclic 4- to hexamer was synthesized in a stepwise manner by Erer et al. and identified for the first time (H. Kaemmerer, G. Happel, VB
ohmer, D. Rathay, Monatsh. Chem., 109,767, (1978)).
Further, Gutsche et al. Made it possible to synthesize 4,6,8-mers in a single step with good yield from p-tert-butylphenol and formaldehyde (CDGutsche, Acc. Che.
m. Res., 16, 161, (1985)). This has facilitated the supply of calixarene, and has led to detailed studies on the production methods, structures, and properties of various calixarene derivatives.

The calixarene has the following features. By changing the number of phenol ring members,
Conformation can be controlled in which compounds having different pore sizes can be synthesized, various functional groups can be introduced using a phenolic hydroxyl group, and various functional groups can be introduced by an aromatic substitution reaction. By properly applying these features, the interaction with various ions and molecules can be controlled, so calixarene derivatives are the `` third inclusion compounds '' next to crown ethers and cyclodextrin-based host compounds, It attracts attention as a leading research material in host-guest chemistry, and is expected as a variety of functional materials in practical use.

[0004] In order to meet such demands, an alkyl group, an ester group and a phenolic OH group are provided on the bottom edge (often referred to as lower rim) where the phenolic OH group is present and on the opposite upper edge (upper rim) side. Many calixarene derivatives into which ether groups or other various functional groups are introduced have been obtained. For example, it has been found that a calixarene derivative in which the OH group on the lower rim side is substituted with an ester group or an ether group functions as an ionophore having excellent recognition ability for metal ions.

[0005]

However, most of these calixarene derivatives have a problem that they are very difficult to handle because they are hardly soluble and have a high melting point. This is due to the structural hardness of calixarene itself, but calixarene has a trade-off problem in that this structural hardness expresses the characteristics as a host molecule.

That is, none of the conventional calixarene derivatives satisfying both "excellent characteristics as a host molecule" and "ease of handling such as good solubility and low melting point" has not been developed yet.

[0007]

Means for Solving the Problems and Effects of the Invention As the present inventors continued research on calixarenes,
The present inventors have found a calixarene derivative having extremely unique properties that solves the above-mentioned problems encountered in conventional calixarene derivatives.

That is, the present invention provides a calixarene derivative represented by the following general formula [1].

[0009]

Embedded image

In the above general formula (I), l, m and n
Is an integer of 0 to 7, respectively. Where l + m + n
Is 3 to 7. n is often 0. That is, the present invention is a calixarene derivative having 4 to 8 phenol rings.

In the above formula, X ¹ and X ² are an atomic group represented by —R or —OR. Here, R represents a relatively long chain, that is, an alkyl group, an alkenyl group, an alkynyl group or a hydroxyalkyl group having 6 to 22 carbon atoms, and is preferably an alkyl group. R is generally a linear group, but may be branched. X ¹ and X ² are generally the same as each other, but may be different.

In the formula, Y ¹ and Y ² represent —CH ＝
_{N -, - CH 2 -NH -} , - CH = CH -, - N = N
-, -CO-O- and -NO = N- (azoxy group). Y ¹ and Y ² are generally the same as each other, but may be different.

Further, in the above general formula [Chemical formula 1], Z ¹ ,
Z ² and Z ³ represent —OH or a substituent thereof. That is, Z ¹ , Z ² and Z ³ are lox of calixarene.
It indicates a phenolic OH group in werrim or various functional groups which have been conventionally substituted / introduced into the OH group according to the intended function of calixarene. Accordingly, examples of such substituents include -OR ¹ , -OCH ₂
COOR ² , OCH ₂ COR ³ , or —OCH ₂ CONR
⁴ ₂ can be cited (wherein, R ^1, R ^2, R ³ and R ⁴ represents a linear or branched alkyl group, alkenyl group,
It is an alkynyl group or a hydroxyalkyl group, which has 1 to 18 carbon atoms, but generally has 1 to 10 carbon atoms. Preferred examples of Z ^1, Z ² and Z ³ are -OCH _3.

Surprisingly, it has been found that the calixarene derivative represented by the general formula (1) described above has excellent solubility, a remarkably reduced melting point, and exhibits flow birefringence. Was. That is, the calixarene derivative of the present invention is highly soluble in many solvents, has a melting point lower by at least about 100 ° C. or more than the parent compound (calixarene serving as a starting material), and is close to the melting point. Shows flow birefringence. Here, the term “flow birefringence” means that molecular orientation occurs along a flow generated by the application of an external stress, and a birefringence phenomenon is observed.

Although the reason why such a property is expressed in the calixarene derivative of the present invention is not fully understood, Y ¹ and Y ² are located on the upper rim side of the calixarene structure via an aromatic ring. And X ¹ and X ² are presumed to be derived from the characteristic structure.

In the calixarene derivative of the present invention, R of -R or -OR constituting X ¹ and X ² has a relatively long chain, that is, 6 to 22 carbon atoms, preferably 8 to 8 carbon atoms.
16 alkyl groups, alkenyl groups, alkynyl groups or hydroxyalkyl groups. When R is short, no lower melting point occurs and no fluid birefringence is exhibited. As R, an optimum group for obtaining a desired calixarene derivative is selected according to Y ¹ and Y ^{2, the} number of phenol ring members, and the like. Generally speaking, it is preferable that the total carbon number of R is 4 to 18 times the number of rings (l + m + n + 1) of the calixarene. When the total number of carbon atoms is smaller than four times the number of rings, the effect of introducing the R group is hardly exhibited, and the melting point does not decrease. Also 18
If it is larger than twice, the mobility of the R group itself decreases, and similarly, the melting point does not decrease.

When Y ¹ and Y ² are —CH ＝ N— (azomethine group) or its reduced form —CH ₂ —NH—, R constituting X ¹ and X ² has 8 to 16 carbon atoms. Is particularly preferred. For example, calix [4] arene having a phenolic OH group substituted with a methoxy group (ie, Z ¹ , Z ² , Z ³ ＯOCH ₃ , 1 + m + n =
3, n = 0) and dodecyl aniline bonded to a calixarene derivative (that is, Y ¹ and Y ² are —CH
= N-, X ¹ and X ² are C ₁₂ H ₂₅₎ has a favorable property of exhibiting very clear flow birefringence in a wide temperature range started showing fluidity, of 5 to 40 ° C. below room temperature ing.

Generally, the structure of the linking group of Y ¹ and Y ² does not contribute as much as R constituting X ¹ and X ² , but is related to the melting point. When X ¹ , X ² and Z ¹ , Z ² , and Z ³ are fixed to specific ones and Y ¹ and Y ² are changed, the effect of lowering the melting point is as follows: —CH ＝ CH — <— NO = N -(Azoxy group) <-N = N-<-CH = N-<-CO-O <-CH
It increases in the order of _2- NH-, but not so much.

The calixarene derivative of the present invention can be used in various applications by utilizing its unique properties.
Hereinafter, such an application will be described, but the application of the present invention is not limited to the following.

When the calixarene derivative of the present invention is sandwiched between polarizing plates orthogonal to each other at a temperature in which the liquid (isotropic) state is exhibited, birefringence appears when an external stress is applied and birefringence appears. Pass between the polarizing plates. Therefore, the calixarene derivative of the present invention can be used, for example, as a display or a pressure sensor in which stress causes molecular orientation as an external field. In this case, when the calixarene derivative of the present invention is used, the response is based on the change from the isotropic phase (liquid) to the birefringent phase, so that the response is compared with the liquid crystal display based on the change from the birefringent phase to the birefringent phase. As a result, a display having a clear contrast with a large difference in the amount of transmitted light when light is turned on and off is obtained. Further, a liquid crystal display requires a pretreatment for causing molecular orientation from the beginning, but the display of the present invention has an advantage that such an orientation treatment does not need to be performed.

As another application example, a stress is applied to the compound of the present invention sandwiched between polarizing plates orthogonal to each other at an isotropic phase temperature, and the temperature is lowered to a melting point or lower while the orientation by flow is generated. Then, the molecules of the compound are fixed while being oriented, and exhibit permanent birefringence, so that light can pass through orthogonal polarizing plates. If this is placed in an environment at or above the melting point, the birefringence immediately disappears and light cannot pass. By using this, various temperature sensors corresponding to the melting point of the compound can be produced. By combining several compounds having different melting points, an element that loses light transmittance at an arbitrary temperature can be produced. These can be used as a maximum thermometer or the like.

Further, since the conventional calixarene derivative has low solubility, it was difficult to obtain a uniform coating film. On the other hand, since the calixarene derivative of the present invention has good solubility, a uniform coating film can be formed by means such as dissolving in a suitable volatile solvent and coating. At this time, when the initial coating is performed under a temperature condition equal to or lower than the melting point to form an emulsion coating film, a transparent coating film is obtained by increasing the temperature. Since such a phenomenon can be reversibly reproduced at the melting point, it is considered that the phenomenon can be applied to a display element that does not use a temperature sensor or a polarizing plate.

Furthermore, the present invention maintains the structural characteristics of calixarene itself,
Provided is a calixarene derivative which has excellent solubility and a low melting point and is easy to handle without impairing the function inherently possessed by the calixarene structure. For example, lower
According to the present invention, by replacing the phenolic hydroxyl group of the rim with a functional group as described above, which is known in the art, while maintaining the ability to selectively bind a specific metal ion, the upper rim is added to the rim according to the present invention. By arranging Y ¹ and Y ² and X ¹ and X ² via an aromatic ring as shown in the general formula [Chemical formula 1], a calixarene derivative having an extremely low melting point can be obtained.

The calixarene derivative of the present invention can be produced by devising a known synthesis method. For example, if Y ¹ and Y ² are -N = N-, or -N
The synthesis method in the case of O = N- group is as shown in the scheme of FIG.

That is, an aromatic amine such as (1) is dissolved in an excess of an acid, and an aqueous solution of sodium nitrite is added dropwise while cooling to prepare a diazonium salt (2). This is reacted with calix [n] arene (3) under basicity to form an azo compound, which is further alkyl or alkenyl,
Alternatively, the target product (6) can be produced by reacting an alkynyl halide.

The diazotization reaction of the compound (1) is generally carried out by dissolving it in an inorganic acid or suspending it in the form of a salt and adding sodium nitrite to react. The theoretical required amount of the acid is 2 equivalents, but preferably 2.5 to 3 equivalents are used in order to prevent by-products of the diazoamino compound. Sodium nitrite is used in an equivalent amount, and excess nitrite is decomposed by adding sulfamic acid, urea and the like. Reaction temperature is usually 0-1
It is preferred to carry out between 5 ° C. Examples of the inorganic acid used here include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and tetrafluoroboric acid.

In the reaction of the compounds (2) and (3), the form active in the reaction is a phenolate ion, so that calix [n] arene is generally made into a solution under basicity, and sometimes sodium bicarbonate and acetic acid are used. The coupling reaction is carried out by adding a buffer such as sodium and adding a weakly alkaline diazonium salt. As the solvent, a polar solvent such as methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide and the like, and a mixed solvent system of these and water are preferable. When a diazonium salt containing a non-nucleophilic anion such as tetrafluoroborate is used, it can be easily coupled with calix [n] arene in the presence of pyridine in a solvent such as tetrahydrofuran or dimethylformamide.

Azocalix [n] arene (4) and R
¹ reaction of X (5) is preferably in the presence of a base, at room temperature to
The reaction is performed at a temperature up to the boiling point of the solvent. Examples of the base used herein include alkali hydroxides such as potassium hydroxide and sodium hydroxide: alkali carbonates such as potassium carbonate and sodium carbonate: alkali metal hydrides such as sodium hydroxide: lithium alkylates such as butyl lithium, and the like. No. As the solvent, acetone, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like are preferable.

When the o-substituted azocalix [n] arene (6) is oxidized with H ₂ O ₂ or the like, azoxycalix [n] arene (7) can be produced.

FIG. 2 shows a synthesis method when Y ¹ and Y ² are —N ＝ CH— groups.

That is, the nitro group of the p-nitrocalix [n] arene of (8) is reduced to an amino group with a reducing agent, and p-formylalkylbenzene (10) is introduced into this to obtain the desired product (11). Can be manufactured.
As the reducing agent used in the reduction of (8), a reducing agent that reduces a nitro group of an aromatic nitro compound to an amino group can be used arbitrarily. For example, iron chloride and hydrazine hydrate as catalysts can be used. Preferably, it is used in the presence of activated carbon. Further, as the solvent to be used, methylcellolylbu is preferable.

The reaction of the compounds (9) and (10) is carried out in a solvent such as benzene which can be azeotroped with water, or by suspending a dehydrating agent such as silica gel, molecular sieves, MgSO ₄ or Na ₂ SO _4. The reaction is performed in a solvent that has been dissolved.

The production method will be described in more detail along the following compound [Chemical Formula 2] which is a preferred example of the calixarene derivative according to the present invention.

[0034]

Embedded image

The reaction scheme is roughly as shown in FIG.

That is, the calix [n] arene (3) is reacted with an alkyl or alkenyl or an alkynyl halide (4), and then the resulting compound (5) is formylated to obtain a compound (6). The compound (6) and the p-alkyl or alkenyl, or alkynyl or alkoxyaniline (7) are dehydrated and condensed to produce the compound (2) (the above [Chemical Formula 2]).

The reaction of the compounds (3) and (4) is preferably carried out in the presence of a base at a temperature from room temperature to the boiling point of the solvent.
The reaction is carried out for about 20 hours. Examples of the base used herein include alkali hydroxides such as potassium hydroxide and sodium hydroxide; alkali carbonates such as potassium carbonate and sodium carbonate; alkali metal hydrides such as sodium hydroxide; lithium alkylates such as butyl lithium and the like. No. Any solvent can be used as long as it does not inhibit the desired reaction, but acetone, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like are particularly preferably used. In order to avoid extra side reactions, it is desirable to carry out the reaction in an inert atmosphere such as nitrogen gas. Compound (5)
Examples of the formylation reaction include a Vilsmeier reaction using N, N-dimethylformamide and phosphorus oxychloride, and a Duff reaction using hexamethylenetetramine and trifluoroacetic acid.

As the compound (7), a linear or branched alkyl group, alkenyl group, alkynyl group or hydroxyalkyl group having 1 to 22 carbon atoms corresponding to R ² in the general formula [Chemical Formula 2] can be used. Any aniline may be used.

The reaction of the compounds (6) and (7) is carried out in a solvent such as benzene which can be azeotroped with water, or by suspending a dehydrating agent such as silica gel, molecular sieves, MgSO ₄ or Na ₂ SO _4. The reaction is performed in a solvent that has been dissolved.

A calixarene derivative in which Y ¹ and Y ² are —CH ₂ —NH— (or —NH—CH ₂ —) is
It can be obtained by reducing the compound of (11) shown in FIG. 2 or FIG. 3 or the compound of (2) using an appropriate reducing agent. Hereinafter, the present invention will be described along with examples in order to further clarify the features of the present invention.

[0041]

EXAMPLE A calixarene derivative [formula 11] of the present invention was produced according to the flowchart shown in FIG.

Production Example 1 : Production of Intermediate [Chemical Formula 9] 4.52 g (5.3 mmol) of calix [8] arene, 7.5 g (315 mmol) of sodium hydroxide,
200 ml of tetrahydrofuran and 68.4 g (475 mmol) of methyl iodide and 10 ml of N, N-dimethylformamide, also dried
Into a mixed solvent consisting of
The mixture was refluxed for 5 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was poured with 500 ml of water and extracted with 500 ml of chloroform. The organic layer was separated, washed four times with 500 ml of water, and dried over magnesium sulfate. After the solution was concentrated, it was treated with methanol to obtain a white solid. The solid was further recrystallized from a mixed solvent of chloroform and methanol to obtain a pure intermediate [Chemical formula 9] (compound (9) in FIG. 4) (white crystals, 4.0 g, yield 79%). .

[0043]

Embedded image

¹ H-NMR (CDCl ₃ , 30 ° C.) δ6.87 (s, 3H, ArH), 4.
04 (s, 2H, ArCH ₂ Ar), 3.51 (s, 3H, ArOCH ₃ ); HPLC (CHCl ₃ , si
lica, 0.5ml / min., 254nm) 6.6min.

Production Example 2 : Production of Intermediate [Chemical Formula 10] 3.80 g of octamethoxycalix [8] arene
(3.96 mmol), hexamethylenetetramine 42
g (300 mmol) in 200 ml of trifluoroacetic acid and the solution is added under nitrogen at 90-112 ° C. for 8 hours.
The mixture was refluxed for 0 hours. The reaction mixture was poured into 500 ml of ice water, stirring was continued for 1 hour, and the mixture was extracted three times with 200 ml of chloroform. The organic layer was washed four times with 500 ml of water, and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain about 5 g of a pale yellow solid. This residue was dissolved in a small amount of a chloroform-n-hexane mixed solvent,
Using a mixed solvent of chloroform: n-hexane (4: 1) as a developing solvent, the mixture was separated and purified on a column packed with silica gel (Wakogel c-300) to give a pure intermediate.
(Compound (10) in FIG. 4) (white powder, 550 mg,
Yield 12%).

[0046]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 9.67 (s, 1 H, Ar-CHO), 7.43 (s, 2 H, A
rH), 4.12 (s, 2H , ArCH 2 Ar), 3.64 (s, 3H, ArOCH 3); HPLC (C
HCl ₃ , silica, 1.5ml / min., 254nm) 12.7min.

Preparation Example 3 Preparation of Compound [Chemical Formula 11] p-Formyl-o-methylcalix [8] arene 7
4 mg (0.0625 mmol), 156 mg (0.5 mmol) of hexadecylaniline, and 1.5 g of molecular sieves 4A1 / 16 were added to 8 g of chloroform, and the solution was heated to reflux under a nitrogen stream for 20 hours.
After filtration of the reaction mixture, the solvent was distilled off under reduced pressure to give about 200
mg of yellow viscous material were obtained. This is further added to chloroform-
Recrystallization from a mixed solvent of methanol gave a pure compound [Chemical formula 11] (compound (11) in FIG. 4) (pale yellow-brown viscous solid).

[0048]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.14 (s, 1 H, ArCH = N), 7.46 (s, 2 H, A
rH), 6.98 (b, 4H , AniH), 4.03 (b, 2H, ArCH 2 Ar), 3.47 (s, 3
H, ArOCH ₃ ), 2.52 (b, 2H, ArC H ₂ CH ₂ ), 1.54 (s, 2H, ArCH ₂ C
_{H 2), 1.22 (s,} 26H, C 13 H 26), 0.85 (m, 3H, CH 3); HPLC (CHCl
₃ , silica, 0.5ml / min., 254nm) 5.1min.

Physical property measurement example 1 : Thermal analysis of compound [Chemical formula 11] 3.84 mg of the compound [Chemical formula 11] obtained in Production example 3 was added to 1
Weigh into a 5 μl Ag sealed cell and heat up at a rate of 1.0
° C / min. DSC measurement was performed in the range of −30 ° C. to 90 ° C. (seiko, DSC120). This compound [formula 11] has about 1
It has a plurality of endothermic peaks from 5 ° C to 55 ° C, and is an isotropic liquid at 55 ° C or higher. Considering that the melting point of the intermediate [Chemical Formula 10] is 275 to 280 ° C, the introduction of the p-hexadecylphenyl group via an azomethine bond lowers the melting point by nearly 250 ° C. In addition, the compound [Chemical Formula 11] not only has a dramatic decrease in melting point, but also has a drastically increased solubility in a solvent, making the compound extremely easy to handle. Figure 5 shows the DSC chart
Shown in Further, the compound showed a flow birefringence in an isotropic phase near the melting point.

Preparation Example 4 Preparation of Compound [Chemical Formula 12] The same procedure as in Preparation Example 3 was carried out except that octylaniline 100 mg was used instead of hexadecylaniline 156 mg in Preparation Example 3, to obtain the following compound. The compound represented by was obtained.

[0051]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.5 (s, 2 H, Ar
H), 7.0 (q, 4H , AniH), 4.1 (b, 2H, ArCH 2 Ar), 3.5 (s, 3H, ArO
_{CH 3), 2.6 (t,} 2H, ArC H 2 CH 2), 1.6 (b, 2H, ArCH 2 C H 2), 1.3
_{(s, 10H, C 5 H} 10), 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.5
ml / min., 254 nm) 5.5 min .; DSC (1 ° C / min.) 67 ° C (top of endothermic peak), 1 mj / mg or less

Preparation Example 5 Preparation of Compound [Chemical Formula 13] The same procedure as in Preparation Example 3 was carried out except that 132 mg of dodecylaniline was used instead of 156 mg of hexadecylaniline in Preparation Example 3, to obtain a compound of the following formula. The compound represented by was obtained.

[0053]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.5 (s, 2 H, Ar
H), 7.0 (s, 4H , AniH), 4.1 (b, 2H, ArCH 2 Ar), 3.5 (s, 3H, ArO
_{CH 3), 2.6 (t,} 2H, ArC H 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.3
_{(s, 18H, C 9 H} 18), 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.5
ml / min., 254 nm) 5.3 min .; DSC (1 ° C / min.) 54 ° C, 1 mj / mg or less

Production Example 6 Production of Compound [Chemical Formula 14] Except that 150 mg of tetradecylaniline was used instead of 156 mg of hexadecylaniline in Production Example 3,
By performing the same operation as in Production Example 3, a compound represented by the following formula [Formula 14] was obtained.

[0055]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.1 (s, 1 H, ArCH = N), 7.5 (s, 2 H, Ar
H), 7.0 (q, 4H , AniH), 4.0 (b, 2H, ArCH 2 Ar), 3.5 (s, 3H, ArO
_{CH 3), 2.5 (t,} 2H, ArC H 2 CH 2), 1.5 (m, 2H, ArCH 2 C H 2), 1.3
_{(s, 22H, C 11 H} 22), 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.
5ml / min., 254nm) 5.1min.; DSC (1 ℃ / min.) 47 ℃, 1mj / mg or less

Production Example 7 Production of Intermediate [Formula 15] o-Methylcalix [6] arene Preparation Example 7 was repeated except that calix [6] arene was used in place of calix [8] arene in Production Example 1. By performing substantially the same operation, o-methylcalix [6] arene [formula 15] was obtained.

[0057]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.95 (m, 3H, ArH), 3.95 (s, 2H, ArCH
_{2 Ar), 3.19 (s,} 3H, ArOCH 3); HPLC (CHCl 3, silica, 1.0ml / m
in., 254nm) 3.6min.

Production Example 8 Preparation of Intermediate [Chemical Formula 16] p-Formyl-o-methylcalix [6] arene Hexamethoxycalix [6] arene was used in place of octamethoxycalix [8] arene in Production Example 2. Otherwise, the same operation as in Production Example 2 was performed, and p
-Formyl-o-methylcalix [6] arene [Formula 16] was obtained (yield 32%).

[0059]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 9.70 (s, 1 H, ArCHO), 7.45 (s, 2 H, Ar
H), 4.06 (s, 2H , ArCH 2 Ar), 3.49 (s, 3H, ArOCH 3); HPLC (CH
(Cl ₃ , silica, 1.5ml / min., 254nm) 8.7min.

Production Example 9 : Production of Compound [Chemical Formula 17] p-formyl-o-methylcalix [6] arene 1
48 mg (0.17 mmol), 317 mg (1 mmol) of hexadecylaniline and molecular sieves 4
Add 1.5 g of A1 / 16 into 15 g of chloroform,
This solution was heated and refluxed for 11 hours under a nitrogen stream. After filtering the reaction mixture, the solvent was distilled off under reduced pressure to obtain a yellow viscous substance. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a pure compound [formula 17].

[0061]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.23 (s, 1 H, ArCH = N), 7.55 (s, 2 H, A
rH), 7.09 (s, 4H , AniH), 4.05 (b, 2H, ArCH 2 Ar), 3.40 (s, 3
H, ArOCH ₃ ), 2.59 (t, 2H, ArC H ₂ CH ₂ ), 1.57 (b, 2H, ArCH ₂ C
_{H 2), 1.26 (s,} 26H, C 13 H 26), 0.88 (t, 3H, CH 3); HPLC (CHCl
₃ , silica, 0.5ml / min., 254nm) 5.6min.; DSC (1 ℃ / min.) 40
℃, 8.4mj / mg

Production Example 10 : Production of Compound [Chemical Formula 18] Except that 289 mg of tetradecylaniline was used instead of 317 mg of hexadecylaniline in Production Example 9,
The same operation as in Production Example 9 was performed to obtain a compound represented by the following formula [Formula 18].

[0063]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.24 (s, 1 H, ArCH = N), 7.55 (s, 2 H, A
rH), 7.08 (s, 4H , AniH), 4.05 (b, 2H, ArC H 2 CH 2), 3.40 (b,
3H, ArOCH ₃ ), 2.50-2.65 (t, 2H, ArC H ₂ CH ₂ ), 1.58 (s, 2H, Ar
_{CH 2 C H 2), 1.26} (s, 22H, C 11 H 22), 0.87 (t, 3H, CH 3); HPLC
(CHCl ₃ , silica, 0.5ml / min., 254nm) 5.3min .; DSC (1 ° C / mi
n.) 47 ℃, 3.8mj / mg

Production Example 11 : Production of Compound [Chemical Formula 19] The same procedure as in Production Example 9 was carried out, except that 262 mg of dodecylaniline was used instead of 317 mg of hexadecylaniline in Production Example 9, to obtain a compound of the following formula. The compound represented was obtained.

[0065]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.23 (s, 1 H, ArCH = N), 7.55 (s, 2 H, A
rH), 7.09 (s, 4H , AniH), 4.05 (s, 2H, ArCH 2 Ar), 3.40 (s, 3
H, ArOCH ₃ ), 2.59 (t, 2H, ArC H ₂ CH ₂ ), 1.59 (m, 2H, ArCH ₂ C
_{H 2), 1.26 (s,} 18H, C 9 H 18), 0.88 (t, 3H, CH 3); HPLC (CHC
l ₃ , silica, 0.5ml / min., 254nm) 5.4min.; DSC (1 ℃ / min.) 4
2 ℃, 2.2mj / mg

Production Example 12 : Production of Compound [Chemical Formula 20] The same operation as in Production Example 9 was carried out except that 205 mg of octylaniline was used instead of 317 mg of hexadecylaniline in Production Example 9, and the following formula was used. The compound represented by was obtained.

[0067]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.24 (s, 1 H, ArCH = N), 7.55 (s, 2 H, A
rH), 7.09 (s, 4H , AniH), 4.05 (s, 2H, ArC H 2 CH2), 3.40 (s,
3H, ArOCH ₃ ), 2.59 (t, 2H, ArCH ₂ C H ₂ ), 1.62 (m, 2H, ArCH ₂ C H
_{2), 1.27 (s, 10H} , C 5 H 10), 0.87 (t, 3H, CH 3); HPLC (CHCl 3,
silica, 1.5 ml / min., 254 nm) 1.9 min .; DSC (1 ° C./min.) 56
℃, 3.5mj / mg

Production Example 13 Preparation of Intermediate [Chemical Formula 21] o-Methylcalix [4] arene 6.0 g (14.2 mmol) of calix [4] arene, 5.4 g (225 mmol) of sodium hydride,
And 82.1 g (570 mmol) of methyl iodide were added to a mixed solvent consisting of 270 ml of dried tetrahydrofuran and 30 ml of N, N-dimethylformamide, which had been dried.
The mixture was refluxed for 8 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was poured with 500 ml of water and extracted with 500 ml of chloroform. The organic layer was separated, washed four times with 500 ml of water, and dried over magnesium sulfate. After distilling off chloroform and washing the crude crystals with methanol,
Recrystallization from a mixed solvent of chloroform-methanol gave a pure intermediate [formula 21] (white crystals, 5.73 g, yield 8).
4%).

[0069]

Embedded image _{^{1 H-NMR (CDCl 3,}} 30 ℃) δ6.4~7.2 (b, 3H, ArH), 3.0~4.6
(b, 5H, ArC H ₂ Ar, ArOCH ₃ ); HPLC (CHCl ₃ , silica, 0.5 ml / mi
n., 254nm) 6.24min.

Production Example 14 : Preparation of an intermediate [formula 22] p-formyl-o-methylcalix [4] arene 4.0 g of tetramethoxycalix [4] arene
(8.3 mmol), 42 g of hexamethylenetetramine
(300 mmol) in 200 ml of trifluoroacetic acid and the solution is added at 90 ° -100 ° C. under a stream of nitrogen.
The mixture was heated under reflux for 4 hours. The reaction mixture was poured into 500 ml of ice water, stirring was continued for 1 hour, and the mixture was extracted three times with 200 ml of chloroform. The organic layer was washed four times with 500 ml of water, and then dried over magnesium sulfate. The solvent was evaporated and concentrated under reduced pressure, and n-hexane was added thereto to obtain 4.63 g of a solid. Recrystallized from chloroform-n-hexane, 3.5
2 g (yield 72%) of white crystals of the intermediate [formula 22] were obtained.

[0071]

Embedded image

Production Example 15 : Production of Compound [Formula 23] p-Formyl-o-methylcalix [4] arene 1
48 mg (0.25 mmol), 317 mg (1 mmol) of hexadecylaniline, and 1.5 g of molecular sieves 4A1 / 16 were added to 16 g of chloroform, and this solution was heated to reflux under a nitrogen stream for about 40 hours.
After filtering the reaction mixture, the solvent was distilled off under reduced pressure to obtain an emulsion glassy solid. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a pure compound [Formula 23].

[0073]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.3-7.8 (b, 2
H, ArH), 7.0 (s, 4H, AniH), 2.8-4.5 (m, 5H, ArCH ₂ Ar / ArOCH
_{3), 2.6 (t, 2H} , ArC H 2 CH 2), 1.6 (b, 2H, ArCH 2 C H 2), 1.2 (s, 2
_{6H, C 13 H 26),} 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.5ml
/min.,254nm) 5.5min .; DSC (1 ℃ / min.) 45 ℃, 44mj / mg

Production Example 16 : Production of Compound [Chemical Formula 24] The same operation as in Production Example 15 was carried out except that 298 mg of tetradecylaniline was used instead of 317 mg of hexadecylaniline in Production Example 15, and the following formula was used. ]
The compound represented by was obtained.

[0075]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.4-7.8 (b, 2
H, ArH), 7.0 (s, 4H, AniH), 3.0-4.4 (m, 5H, ArCH ₂ Ar / ArOCH
_{3), 2.6 (t, 2H} , ArC H 2 CH 2), 1.5 (s, 4H, ArCH 2 C H 2), 1.3 (s, 2
_{0H, C 10 H 20),} 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.5ml
/min.,254nm) 5.5min .; DSC (1 ℃ / min.) 28 ℃, 24.8mj / mg

Production Example 17 : Production of Compound [Chemical Formula 25] The same operation as in Production Example 15 was carried out except that 262 mg of dodecylaniline was used instead of 317 mg of hexadecylaniline in Production Example 15, and the following formula was used. The compound represented by was obtained.

[0077]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.3-7.8 (b, 2
H, ArH), 7.0 (s, 4H, AniH), 3.0-4.6 (m, 5H, ArCH ₂ Ar / ArOCH
_{3), 2.6 (t, 2H} , ArCH 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.3 (s, 1
_{8H, C 9 H 18),} 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica, 0.5ml /
min., 254nm) 5.6min .; DSC (1 ℃ / min.) 20 ℃, 2.7mj / mg

Production Example 18 : Production of Compound [Chemical Formula 26] The same procedure as in Production Example 15 was carried out except that 205 mg of octylaniline was used instead of 317 mg of hexadecylaniline in Production Example 15, and the following formula was used. The compound represented by was obtained.

[0079]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 1 H, ArCH = N), 7.3-7.8 (b, 2
H, ArH), 6.8-7.2 (s, 4H, AniH), 3.0-4.6 (m, 5H, ArCH ₂ Ar / A
_{rOCH 3), 2.6 (t,} 2H, ArC H 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.
_{3 (s, 10H, C 5} H 10), 0.9 (t, 3H, CH 3); HPLC (CHCl 3, silica,
0.5ml / min., 254nm) 5.9min .; DSC (1 ℃ / min.) 27 ℃, 3.2mj
/ mg

Production Example 19 : Intermediate [Formula 27] Triformyl-o-methylcalix [6] arene Hexamethoxycalix [6] arene 3.00 g
(4.17 mmol), hexamethylenetetramine7.
30 g (52 mmol) was added to 175 ml of trifluoroacetic acid, and the solution was heated to reflux at 70 ° C. to 80 ° C. for 3 hours under a nitrogen stream. The reaction mixture was poured into 500 ml of ice water, stirring was continued for 1 hour, and the mixture was extracted three times with 200 ml of chloroform. The organic layer was washed four times with 500 ml of water, and then dried over magnesium sulfate. Chloroform was distilled off under reduced pressure to obtain about 4.0 g of a pale yellow transparent solid. This was dissolved in a small amount of a mixed solvent of chloroform-n-hexane, and silica gel (Wakogel c-3) was used as a developing solvent with a mixed solvent of chloroform: n-hexane (7: 3).
(00: 150 g) to obtain a pure intermediate [Formula 27] (white crystals, yield: about 25%).

[0081]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 9.80 (s, 1.5 H, ArCHO), 9.70 (s, 1.5
H, ArCHO), 7.4-7.6 (m, 6H, H -ArCHO), 6.90 (s, 9H, ArH),
_{4.0 (s, 12H, ArCH 2} Ar), 3.30 (d, 18H, ArOCH 3); HPLC (CHC
l ₃ , silica, 1.5ml / min.) 5.9min.

Production Example 20 : Preparation of Compound [Chemical Formula 28] 8 g of 67 mg (0.083 mmol) of an intermediate [Formula 27], 82 mg (0.25 mmol) of hexadecylaniline, and 1.0 g of molecular sieves 4A1 / 16 Of chloroform, and the solution was added under nitrogen stream for about 40 minutes.
Heated to reflux for an hour. After filtering the reaction mixture, the solvent was distilled off under reduced pressure to obtain a viscous pale yellow substance. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a compound [formula 28].

[0083]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.3 (s, 1 H, ArCH = N), 7.6 (b, 2 H, Ar
H), 7.1 (s, 4H, AniH), 6.9 (b, 3H, ArH), 4.0 (s, 4H, ArCH ₂ A
r), 3.1-3.5 (m, 6H, ArOCH ₃ ), 2.6 (t, 2H, ArC H ₂ CH ₂ ), 1.6
(b, 2H, ArCH ₂ C H ₂ ), 1.2 (s, 26H, C ₁₃ H ₂₆ ), 0.9 (t, 3H, CH ₃ );
HPLC (CHCl ₃ , silica, 0.5 ml / min., 254 nm) 5.5 min .; DSC (1
℃ / min.) 27 ℃, 1mj / mg

Production Example 21 : Preparation of intermediate [formula 29] pentaformyl-o-methylcalix [6] arene 2.00 g of hexamethoxycalix [6] arene
(2.78 mmol), hexamethylenetetramine7.
00 g (50 mmol) was added to 35 ml of trifluoroacetic acid, and the solution was heated to reflux at 90 ° C. to 100 ° C. for 30 hours under a nitrogen stream. The reaction mixture was poured into 500 ml of ice water, stirring was continued for 1 hour and extracted with 500 ml of chloroform. The organic layer was washed three times with 500 ml of water, and then dried over magnesium sulfate. Chloroform was distilled off to obtain about 2.5 g of crude crystals. This was dissolved in a small amount of chloroform-n-hexane, and separated and purified on a column packed with silica gel (Wako gel c-300: 150 g) using a mixed solution of chloroform: n-hexane (4: 1) as a developing solvent. Pure intermediate
(White crystals, yield: about 20%).

[0085]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C) δ 9.82, 9.68 (s, 5H, ArCHO), 7.4-7.6
(d, 10H, H ArCHO), 6.90 (s, 3H, ArH), 4.05 (d, 12H, ArC H ₂ A
r), 3.40-3.50 (q, 18H , ArOCH 3); HPLC (CHCl 3, silica, 1.5
ml / min.) 5.9min.

Preparation Example 22 : Preparation of Compound [Chemical Formula 30] 87 mg (0.10 mmol) of the intermediate [Chemical Formula 29], 166 mg (0.5 mmol) of hexadecylaniline, and 10 g of 1.0 g of molecular sieves 4A1 / 16 Of chloroform, and the solution was added under nitrogen stream for about 48 hours.
Heated to reflux for an hour. After filtering the reaction mixture, the solvent was distilled off under reduced pressure to obtain a viscous pale yellow substance. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a compound [Chemical Formula 30].

[0087]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (s, 5 H, ArCH = N), 7.6 (s, 10 H, Ar
H), 7.1 (s, 20H , AniH), 7.0 (b, 3H, ArH), 4.0 (b, 12H, ArCH 2
Ar), 3.3-3.5 (d, 18H, ArOCH ₃ ), 2.6 (t, 10H, ArC H ₂ CH ₂ ),
1.6 (m, 10H, ArCH ₂ C H ₂ ), 1.3 (s, 130H, C ₁₃ H ₂₆ ), 0.9 (t, 15
_{H, CH 3);. HPLC} (CHCl 3, silica, 0.5ml / min, 254nm) 5.3mi
n.; DSC (1.0 ℃ / min.) 38 ℃, 1.1mj / mg

Production Example 23 : Production of Compound [Chemical Formula 31] p-Formyl-o-methylcalix [4] arene 1
48 mg (0.25 mmol), hexadecylaniline 158 mg (0.5 mmol), dodecylaniline 13
1 mg (0.5 mmol) and 1.5 g of Molecular Sieves 4A1 / 16 were added to 16 g of chloroform, and the solution was heated to reflux under a nitrogen stream for about 40 hours.
After filtering the reaction mixture, the solvent was distilled off under reduced pressure to obtain an emulsion glassy solid. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a compound [formula 31].

[0089]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 8.2 (b, 2H, ArCH = N), 7.3-8.0 (b, 4
H, ArH), 6.8-7.3 (b, 8H, AniH), 3.0-4.6 (b, 10H, ArCH ₂ Ar /
_{ArOCH 3), 2.6 (t,} 4H, ArC H 2 CH 2), 1.6 (b, 4H, ArCH 2 C H 2),
_{1.3 (s, 44H, C 13} H 26 / C 9 H 18), 0.9 (t, 6H, CH 3); HPLC (CHC
l ₃ , silica, 0.5ml / min., 254nm) 5.5min .; DSC (1 ℃ / min.) 2
8.8 ℃, 26.1mj / mg

Preparation Example 24 : Preparation of intermediate [Formula 32] p-amino-o-methylcalix [6] arene p-nitro-o-methylcalix [6] arene
9 g was added to 100 ml of methylcellolylbu, and 0.4 g of activated carbon and 0.065 g of ferric chloride hexahydrate were added thereto, followed by heating and stirring at 80 ° C. for 30 minutes. Next, 12 ml of hydrazine monohydrate was added dropwise, and the mixture was further heated and stirred for 5 hours, and then the activated carbon was filtered off while hot. The filtrate was cooled, and the precipitated crystals were collected by filtration, and the intermediate [formula 32] was recrystallized from ethanol (yield 1.5 g).

[0091]

Embedded image

Production Example 25 : Production of Compound [Chemical Formula 33] p-Amino-o-methylcalix [6] arene 13
5 mg (0.167 mmol), 330 mg (1 mmol) of p-formylphenylhexadecane, and 3 g of molecular sieves 4A1 / 16 were added to 16 g of chloroform, and the solution was heated to reflux under a nitrogen stream for 20 hours. After the reaction mixture was filtered, the solvent was distilled off under reduced pressure to obtain about 4
00 mg of a yellow gum was obtained. This was further recrystallized from a mixed solvent of chloroform-methanol to obtain a pure compound [Formula 33].

[0093]

Embedded image _{^{1 H-NMR (CDCl 3,}} 30 ℃) δ8.2 (s, 1H, -CH = N-), 7.6 (s, 4H, RAr
H), 7.0 (s, 2H, CH ₃ OArH), 3.8 (b, 2H, ArCH ₂ Ar), 3.7 (s, 3
H, ArOCH ₃ ), 2.4-2.6 (b, 2H, ArC H ₂ CH ₂ ), 1.6 (b, 2H, ArCH ₂ C
H ₂ ), 1.3 (s, 26H, C ₁₃ H ₂₆ ), 0.8-1.0 (t, 3H, CH ₃ )

Production Example 26 : Production of Compound [Chemical Formula 34] p-Amino-o-methylcalix [6] arene 13
5 mg (0.167 mmol), 218 mg (1 mmol) of p-formylphenyloctadecane, and 3 g of molecular sieves 4A1 / 16 were added to 16 g of chloroform.
4] was obtained.

[0095]

Embedded image _{^{1 H-NMR (CDCl 3,}} 30 ℃) δ8.2 (s, 1H, -CH = N-), 7.6 (s, 4H, RAr
H), 7.0 (s, 2H, CH ₃ OArH), 3.8 (s, 2H, ArCH ₂ Ar), 3.7 (s, 3
H, ArOCH ₃ ), 2.4-2.6 (t, 2H, ArC H ₂ CH ₂ ), 1.6 (b, 2H, ArCH ₂ C
H ₂ ), 1.3 (s, 10H, C ₁₃ H ₂₆ ), 0.8-1.0 (t, 3H, CH ₃ )

Production Example 27 : Production of Compound [Chemical Formula 35] 50 mg of Compound [Chemical Formula 23] was dissolved in 10 g of dried chloroform, and heated under a stream of N ₂ . After reflux had begun, 50 mg of sodium borohydride dissolved in 2 ml of methanol was quickly added to the above solution. About 10
After one minute, the heating was stopped and the mixture was cooled to room temperature. 50 ml of the reaction solution
And washed with water four times, and dried over magnesium sulfate.
The dried reaction solution was concentrated under reduced pressure, and about 10 ml of M
MeOH was added to obtain the desired compound (35) as a precipitate. This was further reprecipitated from a mixed solvent of chloroform-methanol to obtain a pure compound of the following formula.

[0097]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.8-7.2 (d, 4H, AniH), 6.4-6.8 (b, 2
H, ArH), 2.8-4.6 (m, 8H, ArCH ₂ Ar / ArOCH ₃ / ArCH ₂ NH), 2.3-2.
7 (t, 2H, ArC H 2 CH), 1.6 (b, 2H, ArCH 2 C H 2), 1.2 (s, 26H, C 13 H
_{26), 0.8-1.0 (t, 3H} , CH 3); HPLC (CHCl 3: MeOH = 9: 1, silica,
(0.5ml / min., 254nm) 5.2min.

Production Example 28 : Production of Compound [Chemical Formula 36] The same operation as in Production Example 27 was carried out except that the compound of Chemical Formula 24 was used instead of the compound of Chemical Formula 23 in Production Example 27, A compound represented by the formula [Formula 36] was obtained.

[0099]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.8-7.2 (d, 4H, AniH), 6.3-6.8 (b, 2
H, ArH), 2.8-4.6 (m, 8H, ArCH ₂ Ar / ArOCH ₃ / ArCH ₂ NH), 2.3-2.
6 (t, 2H, ArC H 2 CH 2), 1.6 (b, 2H, ArCH 2 C H 2), 1.2 (s, 22H, C 11 H
_{22), 0.8-1.0 (t, 3H} , CH 3); HPLC (CHCl 3: MeOH = 9: 1, silica,
(0.5ml / min., 254nm) 5.3min.

Production Example 29 : Production of Compound [Chemical Formula 37] The same procedures as in Production Example 27 were carried out except for using the compound of Chemical Formula 25 instead of the compound of Chemical Formula 23 in Production Example 27, A compound represented by the formula [Formula 37] was obtained.

[0101]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.8-7.2 (d, 4H, AniH), 6.3-6.8 (b, 2
H, ArH), 2.8-4.6 (m, 8H, ArCH ₂ Ar / ArOCH ₃ / ArCH ₂ NH), 2.3-2.
7 (t, 2H, ArC H 2 CH 2), 1.5-1.7 (b, 2H, ArCH 2 C H 2), 1.2 (s, 18H,
C ₉ H ₁₈ ), 0.7-1.0 (t, 3H, CH ₃ ); HPLC (CHCl ₃ : MeOH = 9: 1, silic
a, 0.5ml / min., 254nm) 5.4min.

Production Example 30 : Production of Compound [Chemical Formula 38] The same operation as in Production Example 27 was carried out except for using the compound of Chemical Formula 26 instead of the compound of Chemical Formula 23 in Production Example 27, A compound represented by the formula [Formula 38] was obtained.

[0103]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.8-7.4 (d, 4H, AniH), 6.3-6.8 (b, 2
H, ArH), 2.8-4.6 (m, 8H, ArCH ₂ Ar / ArOCH ₃ / ArCH ₂ NH), 2.3-2.
6 (t, 2H, ArC H 2 CH 2), 1.5-1.7 (b, 2H, ArCH 2 C H 2), 1.3 (s, 10H,
_{C 5 H 10), 0.7-1.0 (} t, 3H, CH 3); HPLC (CHCl 3: MeOH = 9: 1, silic
a, 0.5ml / min., 254nm) 5.5min.

Production Example 31 : Production of compound [Chemical formula 39] The same operation as in Production example 27 was carried out except that compound [Chemical formula 17] was used instead of compound [Chemical formula 23] in Production example 27, and the following formula [ 39] was obtained.

[0105]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C) δ 6.7-7.1 (t, 4H, AniH), 6.2-6.4 (d, 2
H, ArH), 3.2-4.2 (b , 8H, ArCH 2 Ar / ArOCH 3 / ArCH 2 NH), 2.3-2.
6 (b, 2H, ArC H 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.3 (s, 26H, C 13 H
_{26), 0.8-1.0 (t, 3H} , CH 3); HPLC (CHCl 3: MeOH = 9: 1, silica,
0.5ml / min., 254nm) 4.9min.

Production Example 32 : Production of Compound [Chemical Formula 40] The same procedures as in Production Example 27 were carried out except for using compound [Chemical Formula 18] in place of the compound of [Chemical Formula 23] in Production Example 27, to obtain a compound of the following formula A compound represented by the following formula was obtained.

[0107]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C.) δ 6.7-7.1 (t, 4H, AniH), 6.2-6.5 (d, 2
H, ArH), 3.3-4.2 (b , 8H, ArCH 2 Ar / ArOCH 3 / ArCH 2 NH), 2.3-2.
6 (b, 2H, ArC H 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.3 (s, 22H, C 11 H
_{22), 0.7-1.0 (t, 3H} , CH 3); HPLC (CHCl 3: MeOH = 9: 1, silica,
(0.5ml / min., 254nm) 5.1min.

Production Example 33 : Production of Compound [Chemical Formula 41] The same procedure as in Production Example 27 was carried out except for using Compound [Chemical Formula 19] instead of Compound [Chemical Formula 23] in Production Example 27, to obtain the following formula [ Compound 41] was obtained.

[0109]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C) δ 6.7-7.0 (t, 4H, AniH), 6.2-6.5 (d, 2
H, ArH), 3.3-4.1 (b, 8H, ArCH ₂ Ar / ArOCH ₃ / ArCH ₂ NH), 2.3-2.
6 (b, 2H, ArC H 2 CH 2), 1.6 (s, 2H, ArCH 2 C H 2), 1.2 (s, 18H, C 9 H
_{18), 0.7-1.0 (t, 3H} , CH 3); HPLC (CHCl 3: MeOH = 9: 1, silica,
(0.5ml / min., 254nm) 5.2min.

Production Example 34 : Production of compound [Chemical formula 42] The same operation as in Production example 27 was carried out except that compound [Chemical formula 20] was used instead of compound [Chemical formula 23] in Production example 27, to obtain the following formula [ Compound 42] was obtained.

[0111]

Embedded image ¹ H-NMR (CDCl ₃ , 30 ° C) δ 6.6-7.0 (t, 4H, AniH), 6.2-6.5 (d, 2
H, ArH), 3.3-4.2 (b , 8H, ArCH 2 Ar / ArOCH 3 / ArCH 2 NH), 2.3-2.
6 (t, 2H, ArC H 2 CH 2), 1.5-1.7 (b, 2H, ArCH 2 C H 2), 1.3 (s, 10H,
_{C 5 H 10), 0.7-1.0 (} t, 3H, CH 3); HPLC (CHCl 3: MeOH = 9: 1, silic
a, 0.5ml / min., 254nm) 5.4min.

Preparation Example 35 Preparation of Compound [Chemical Formula 43] 10 mm of dry tetrahydrofuran containing 1.52 g (15 mmol) of diisopropylamine was added.
ol of BuLi in 6.25 ml of a hexane solution are slowly added under ice-cooling. 3.9 g in this reaction solution
10 m containing (15 mmol) p-dodecyltoluene
l of dry tetrahydrofuran solution was added, and stirring was continued for about 1 hour under ice cooling. This was mixed with the intermediate compound (22) p-formyl-O-methylcalix [4] arene (1 g).
(1.75 mmol) is slowly added to 10 ml of a solution of dry tetrahydrofuran under ice-cooling. After about 10 hours, the reaction solution is poured into 100 ml of water and stirred for 30 minutes. The compound was extracted with 400 ml of chloroform,
After washing five times with 700 ml of water, the resultant was dried with magnesium sulfate. The reaction solution was concentrated under reduced pressure, and re-precipitated from a mixed solvent of chloroform-n-hexane to obtain an intermediate 1.35.
g was obtained. 1.35 g of this intermediate was dissolved in 135 ml of trifluoroacetic acid and refluxed for 15 hours. Reaction solution 4
Put into 00 ml of ice water and adjust pH with sodium carbonate
8.0. The mixture was extracted with about 250 ml of chloroform, washed four times with 300 ml of water, and dried over magnesium sulfate. The reaction solution was concentrated under reduced pressure, and reprecipitated from a mixed solvent of chloroform and n-hexane to obtain the following formula [Chemical Formula 4]
750 mg of the pure compound of 3] was obtained.

[0113]

Embedded image

Preparation Example 36 : Preparation of Compound [Chemical Formula 44] In place of p-dodecyltoluene in Preparation Example 35, p
-The same operation as in Production Example 35 was performed except that hexadecyltoluene was used, and a compound 8 represented by the following formula [Formula 44]
00 mg was obtained.

[0115]

Embedded image

Preparation Example 37 Preparation of Compound [Chemical Formula 45] 5.5 mmol of p-dodecylbenzenediazonium tetrafluoroborate and 1.1 mmol of calix [4] arene in a mixed solvent of 20 ml of tetrahydrofuran and 10 ml of pyridine. To obtain azocalix [4] arene. 1.0 g of the present azocalix [4] arene was dissolved in 100 ml of tetrahydrofuran, 2 g of sodium hydride was added thereto, and the mixture was stirred for about 30 minutes. Further, 6 ml of methyl iodide was added, and the mixture was refluxed for 5 hours. The solvent was distilled off under reduced pressure, and 500 ml of water was added to obtain a suspension. From here, chloroform 4
Extraction was performed with 00 ml, washed four times with 500 ml of water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude crystal. By reprecipitating from chloroform-n-hexane, the pure compound 9 represented by the following formula [Formula 45] was obtained.
50 mg could be obtained.

[0117]

Embedded image

Physical Property Measurement Example 2 The physical properties of many compounds obtained in the above Production Examples were measured. The melting point mp was measured using a high sensitivity differential scanning calorimeter (SEIKO DSC 120 type). For this purpose, the Ag cell (1
5 .mu.l), enclose about 5 to 10 mg of the sample, and 1 DEG C./mi
n. The temperature at the peak top of the DSC peak in the temperature raising process (1 ° C./min.) After the temperature was raised / lowered (−30 ° C. to 90 ° C.) once at a speed of mp was defined as mp. Furthermore, observation of the flow birefringence was confirmed under polarized light by an optical microscope.

As shown in Table 1 below, compounds according to the present invention [Chemical Formulas 11 to 14], [Chemical Formulas 17 to 20],
[Formula 23] to [Formula 26], [Formula 28], [Formula 30],
In all of [Chemical Formula 31], [Chemical Formulas 35] to [Chemical Formula 45], the effect of lowering the melting point due to the introduction of the substituent is very remarkably exhibited.

[0120]

[Table 1]

As shown in the above table, it can be seen that the melting point of the compound of the present invention is lower by about 200 to 300 ° C. than that of the parent compound o-methylcalix [n] arene. In addition, the solubility also increased dramatically. Further, it was found that all of these compounds exhibited fluid birefringence in an isotropic phase near the melting point.

Experimental Example 3 An experiment was conducted to further clarify the flow birefringence in the isotropic phase, which is a feature of the calixarene of the present invention. Since the calixarene derivative of the present invention has a slender molecular structure, a molecular orientation occurs along a flow generated by an external stress or the like, and a birefringence phenomenon appears. This flow birefringence can be easily observed under orthogonal polarization by an optical microscope. Further, the birefringence due to the flow disappears with time when the application of the external stress is stopped, but it depends on the temperature due to the molecular motion of the calixarene derivative. Therefore, the behavior of eliminating the flow birefringence under some temperature conditions was observed as follows.

When a sample is sandwiched between two glass plates and the glass plates are shifted with a constant force, flow birefringence can be observed. At this time, if the vibrating surfaces of the two polarizing plates of the microscope are orthogonal to each other, the field is dark when the sample is isotropic, and the field becomes bright when the sample becomes anisotropic. The change in the brightness of the visual field was measured by an exposure meter.

[0124]

[Table 2]

When the reciprocal of the depolarization time is a depolarization rate constant k (sec ⁻¹ ),

[Table 3]

From the Arrhenius equation

(Equation 1)

From the graph, logA = 27.0854 A = 1.22 × 10 ²⁷ ΔH / 2.303R = 8296 ΔH = 37.960 (cal.mol ⁻¹ ) The above results are shown in FIG.

From the above data, the compound of the present invention [Chemical Formula 2]
5] is a pressure sensor or the like at 30 ° C. (about 2 seconds) or higher at which the response is fast, and the response time is long.
It was shown that it can be used as a temporary storage element or the like at a temperature of less than about 1 ° C. (about 1 minute).

Physical property measurement example 4 As described above, the following measurements were performed to confirm that the calixarene derivative of the present invention can be used as a temperature-responsive element such as a maximum thermometer.

The compound [Formula 23] is kept at about 50 ° C. (isotropic liquid) and sandwiched between glass plates. While cooling, a linear stress is applied so that the molecules are oriented in parallel. When this sample is observed under a crossed Nicols with an optical microscope, light is transmitted through the entire surface and looks bright. This state is defined as a transmittance of 100%,
The state of the dark field with the sample removed is set as 0% transmittance,
While measuring the light transmittance with an exposure meter while controlling the temperature with a thermo stage, a high sensitivity differential scanning calorimeter (SEI
DSC measurement was performed using KO DSC 120). FIG. 7 shows the results.

The DSC curve was obtained by enclosing about 5 mg of a sample in an Ag cell (15 μl), adding 1 ° C./min. The temperature is raised and lowered (-30 ° C. to 90 ° C.) once at a rate of
° C / min. ). According to this, it is understood that the transmittance is almost 100% up to the temperature at which the endotherm starts, whereas it returns to night vision at the temperature at which the endotherm ends. From the above data, it was confirmed that the calixarene derivative of the present invention can be used as a temperature-responsive element such as the above-described maximum thermometer.

Physical property measurement example 5 In order to know the properties of the calixarene derivative of the present invention,
The light transmittance was measured with an exposure meter using an optical microscope and a thermostage. The glass plate on which the compound [Chemical Formula 24] was uniformly applied was set to have a visual field brightness of 100% when kept at 40 ° C. by a thermo stage. Next, when the temperature of the thermostage was rapidly cooled to 10 ° C., the coating film of the compound [Chemical Formula 24] became milky turbid, and the amount of light decreased to about 70%. This was reproducible over and over again. FIG. 8 shows the result.

The experimental data confirmed that the calixarene derivative of the present invention can be used as a temperature-responsive display or a temperature sensor without using a polarizing plate as described above.

[Brief description of the drawings]

FIG. 1 shows a synthesis route of a calixarene derivative of the present invention.

FIG. 2 shows a synthesis route of another compound belonging to the calixarene derivative of the present invention.

FIG. 3 shows a synthesis route of a compound having an azomethine group among the calixarene derivatives of the present invention.

FIG. 4 is a flowchart showing a synthesis route of an example of a calixarene derivative of the present invention.

FIG. 5 is an example of a DSC chart when a calixarene derivative of the present invention is thermally analyzed.

FIG. 6 is a graph of an Arrhenius plot for determining the depolarization rate characteristics of the calixarene derivative of the present invention.

FIG. 7 is a diagram showing the temperature response characteristics of the calixarene derivative of the present invention using light transmittance and DSC data.

FIG. 8 is a graph showing the relationship between optical properties and temperature responsiveness of the calixarene derivative of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 215/76 C07C 215/76 217/58 217/58 217/84 217/84 217/92 217/92 245/08 245/08 291/08 291/08 C09K 3/00 C09K 3/00 Z 9/00 9/00 Z // C07C 47/575 C07C 47/575 (56) References Tetrahedron, (1983) 39 (3) p. 409-426 Tetrahedron, (1986) 42 (6) p. 1633-1640 J.P. Inclusion Phenom. , (1986) 4 (3) p. 247-253J. Inclusion Phenom. , (1987) 5 (5) p. 581-590 Tetrahedron, (1989) 45 (7) p. 2177-2182 J.P. Chem. Soc. , Perkin Trans. 1, (1992) (15) p 1885-1887 Chem. Lett. , (1991) P. 2147-2150 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 251/24 C07C 43/21 C07C 69/84 C07C 69/92 C07C 69/94 C07C 215/76 C07C 217/58 C07C 217/84 C07C 217/92 C07C 245/08 C07C 291/08 C09K 3/00 C09K 9/00 C07C 47/575 CAOLD (STN) CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A calixarene derivative represented by the following general formula [1]. Embedded image [Wherein, l, m and n are each an integer from 0 to 7, 1 + m + n = 3 to 7, and X ¹ and X ² are
Are the same or different atomic groups represented by -R or -OR (provided that R is a linear or branched alkyl, alkenyl, alkynyl, or hydroxyalkyl group having 6 to 22 carbon atoms) ), Y ¹ and Y ² are the same or different atomic groups from each other, and —CH ＝ N—, —
_{CH 2 -NH -, - CH =} CH -, - N = N -, - CO
—O— and —NO ＝ N—, wherein Z ¹ , Z ² and Z ³ are the same or different atomic groups from each other;
Or a substituent thereof. ]