JP3525183B2 - Calixus allene compound and process for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a calixarene compound and a method for producing the same.

[0002]

Macrocyclic compounds such as calixarene and calixarene-resorsialene are compounds obtained by condensation reaction from phenol and resorcinol, respectively, and these compounds are used for assembling a molecular system having an elaborate structure. It is used as a component. The reason is that it has delicately constructed three-dimensional voids, can maintain an appropriately rigid three-dimensional structure, is easy to functionalize, and can be synthesized from inexpensive petrochemical raw materials. For example, a calix [n] arene compound and a calix-resorsialene compound can introduce a long-chain aliphatic chain, and many studies have been conducted in the fields of ultra-high polymer chemistry and Langmuir monolayer formation. , The number continues to increase year by year. Furthermore, the molecular material in which calix [4] arene and porphyrin are combined with quinones has attracted attention as an electron transfer device in a homogeneous petroleum solution. Calix [4] arene changes the following two characteristics by changing the number of groups and bonding moieties introduced into the lower side (phenolic hydroxyl group) and the upper side (aromatic nucleus) of the calix [4] arene. Can have an impact. The first feature is the three-dimensional structure unique to calix [4] arene, and the second feature is the supramolecularization function utilizing the three-dimensional vacancy or phenolic hydroxyl group of the compound. At present, attention is being paid to improving the action and ability of higher value-added by variously studying these functional enhancements.

[Chemical 9] Calix [4] arene has four forms and three-dimensional structures. Specifically, cones, partial cones, 1
And positions 2 and 3 are on opposite sides and positions 1 and 3 are on opposite sides.

[Chemical 10] It is the temperature, solution, substituents in the para position, etc. that determine the four morphologies of calix [4] arene. It is already known that controlling such a form is extremely important and necessary for the function to be exerted. Against this background, new attempts are expected.

[0003]

The object of the present invention is to control the three-dimensional structure from calix [4] arene having a specific structure in which two different groups, a formyl group and a nitro group, are allowed to exist opposite to each other. It is an object of the present invention to provide a corn structure derivative of formylnitrocalix and a partial corn structure derivative compound.

[0004]

The present inventors have noticed that it is possible to introduce a formyl group and a nitro group, which are used in the field of supramolecular compounds, into calix [4] arene, Having a formyl group and a nitro group at a specific site on the upper side, 5-formyl-17-nitro2
5,27-Dimethoxycalix [4] arene-26,
A reagent having a 28-diol and an ethylene glycol tetramer, specifically, tetraethylene glycol ditosylate is treated in the presence of a base to have a formyl group and a nitro group on the upper side. 5-formyl-17-nitro 25, 27
-Dimethoxycalix [4] arene-crown-5
(Cone type), similarly, 5-formyl-17-nitro25,27-dimethoxycalix [4] arene 2 having a formyl group and a nitro group at a specific site is obtained.
When 5,28-diol is treated with methyl halide or methyl tosylate in the presence of a base, 5-formyl-17-nitro 25,2 having a formyl group and a nitro group on the upper side is obtained.
The present invention has been completed by finding that 6,27,28-tetratoxicalix [4] arene (cone type) and (partially cone type) can be obtained.

That is, according to the present invention, the following inventions are provided. (1) 5-formyl-1 represented by the following structural formula (1)
7-nitro 25,27-dimethoxycalix [4] arene-crown-5.

[Chemical formula 11] (1) (2) represented by the following structural formula (2): 5-formyl-
17-nitro-25,26,27,28-tetramethoxycalix [4] arene (corn type compound).

[Chemical 12] (2) (3) 5-formyl-1 represented by the following structural formula (3)
7-nitro-25,26,27,28-tetramethoxycalix [4] arene (partially corn type compound).

[Chemical Formula 13] (3) (5) 5-formyl-17-nitro-25,27-dimethoxycalix [4] arene-26,28-diol represented by the following structural formula (4) is reacted with tetraethylene glycol ditosylate, 5-formyl-17-nitro 25,2 represented by the following structural formula (1)
7-Dimethoxycalix [4] arene-crown-5
A method of manufacturing.

[Chemical 14] (4)

[Chemical 15] (1) (6) 5-formyl-1 represented by the following structural formula (4)
5-Formyl-17-nitro 25 represented by the following structural formulas (2) and (3) is obtained by treating 7-nitro 25,27-dimethoxycalix [4] arene 26,28-diol with methyl nitrile. , 26, 2
A method for producing 7,28-tetratoxycalix [4] arene (cone type) and (partially cone type).

[Chemical 16] (4)

[Chemical 17] (2)

[Chemical formula 18] (3)

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The compound obtained in the present invention is a calix [4] arene compound having a specific structure, specifically, 5-formyl-17-nitro25,27-dimethoxycalix represented by the following structural formula 1. [4] Allene-Crown-5. This compound is called a cone type because of its three-dimensional structure, has a formyl group and a nitro group at specific sites on the upper side (positions 5 and 7), and has dimethoxy at a specific site on the lower side. It has a cone-type three-dimensional structure having a group, a hydroxy group, and a crown-5 group.

[Chemical Formula 19] (1)

The compound obtained by the present invention is a calix [4] arene compound having a specific structure, specifically, 5-formyl-17-nitro 25, represented by the structural formulas (2) and (3). 26,27,28-Tetramethoxycalix [4] arene cone type and partial cone type. This compound is called a corn type or a part corn type depending on the characteristics of the three-dimensional structure. The cone type has a formyl group and a nitro group at specific sites (5th and 7th positions) on the upper side and has a methoxy group on the lower side. The partial cone type has a formyl group on the upper side and a methoxy group or a nitro group on a specific site on the lower side.

[Chemical formula 20] (2)

[Chemical 21] (3)

Next, a method for producing the calix [4] arene compound represented by the structural formulas (1), (2) and (3) will be described below. The raw material of the present invention is a compound represented by the following structural formula 5 (wherein R represents a hydrogen atom or a methyl group).

[Chemical formula 22] (5)

Formyl nitrocalix [4] arene represented by the above structural formula 5 is reacted with a tetraethylene glycol agent in the presence of a solvent to obtain a desired compound represented by the following structural formula (1). To manufacture.

[Chemical formula 23] (1)

In this reaction, tetraethylene glycol ditosylate (TsO (CH ₂ CH ₂ O) ₄ Ts) is used as the tetraethylene glycol agent. This reaction is carried out in the presence of a solvent. Specific examples of the solvent include dimethylformamide (DMF), acetonitrile (CH ₃ CN), tetrahydrofuran (THF) and the like. As the basic compound to be added, cesium carbonate, NaH or the like is used. Among these,
Combination of cesium carbonate and DMF, and NaH and DM
A combination of F is preferred. The reaction temperature is preferably performed under gentle reflux (100 ° C.).

When the above formyl nitrocalix [4] arene is treated with methyl halide or methyl tosylate in the presence of a basic compound in a solvent, it is represented by the following structural formulas (2) and (3): Formyl-17
It can be obtained as a mixture containing only -nitro-25,26,27,28-tetramethoxycalix [4] arene (cone type compound) and (partially corn type).

[Chemical formula 24] (2)

[Chemical Formula 25] (3) This reaction is carried out in the presence of a solvent. As a solvent,
Specifically, dimethylformamide (DMF), methyl nitrile (CH ₃ CN), tetrahydrofuran (TH
F) etc. can be mentioned. As the basic compound to be added, potassium carbonate, cesium carbonate, NaH or the like is used. Among these, a combination of potassium carbonate and acetonitrile is preferable. Reaction temperature is 50
It is preferable to carry out the treatment at a temperature of not lower than 0 ° C and under reflux. The reaction product is obtained as a mixture of the above structural formulas (2) and (3).

As described above, according to the method of the present invention, it is possible to obtain only the compound represented by the structural formula (1) or the mixture consisting of the structural formulas (6) and (7). The manufacturing process is shown in the figure as follows.

[Chemical formula 26]

The compounds of the above structural formulas (1), (2) and (3) obtained in the present invention are extremely useful as precursors capable of chemical modification inherent in formyl groups and nitro groups. Furthermore, it has the characteristic that its three-dimensional structure can be changed by incorporating various metal cations in the calixarene molecule.

[0014]

EXAMPLES Example 1 (5-formyl-17-nitro 2
Synthesis of 5,27-dimethoxycalix [4] arene-crown-5). 5-Formyl-17-nitro 25,27-dimethoxycalix [4] arene-26,28-diol 150
mg (0.286 mmol) together with 293 mg (0.899 mmol) of cesium carbonate in DMF60.
Dissolve in ml, stir and hold under reflux, tetraethylene glycol ditosylate 172 mg (0.343 mm
ol) dissolved in 30 ml of THF was added dropwise over 1.5 hours. Subsequently, the reaction was continued while refluxing for 24 hours, the product solution was cooled, treated with 1N hydrochloric acid, and extracted several times with dichloromethane. The extracts obtained were combined, washed with water, and the solvent was removed under reduced pressure. The crude product thus obtained was washed with THF and removed by filtration. The yield of the product represented by Structural Formula 1 is
It was 65%. The structural formula was confirmed from the following results. The properties were as follows. mp> 300 ° C .; 1H-NMR
(CDCl3) δ 3.28 (4H, d, J = 12.9
Hz) 3.58, 3.74, 3.96, 4.00, (e
ach 2H, brs), 4.14 (6H, s) 4.4
5 (4H, d, J = 12.6Hz), 6.96 (2H,
m), 7.08 (2H, s), 7.18-7.25 (4
H, m), 7.41 (2H, s), 9.47 (1H,
s); mass spectrum, m / e 684
(M +). Anal. Calcd for C39H41NO10Na0.6H2O: C, 65.2
8; H, 5.92; N, 1.95. Found: C, 6
5.21: H 2, 5.62; N, 2.03. Thus, 5-formyl-17-nitro 25,2
7-Dimethoxycalix [4] arene-crown-5
(Cone type) was obtained.

[Chemical 27] (1)

Example 2 (Synthesis of 5-formyl-17-nitro-25,26,27,28-tetramethoxycalix [4] arene (cone type compound) and (partially cone type compound)) 5-formyl- 17-nitro 25,27-dimethoxycalix [4] arene-26,28-diol 150 m
g (0.286 mmol), 124 mg of potassium carbonate
60m acetonitrile with (0.899mmol)
1 ml, stirred and kept under reflux, methyl iodide 49 mg (0.286 mmol) was added to THF 30 m.
What was melt | dissolved in 1 was dripped over 1.5 hours. Subsequently, the reaction was continued while refluxing for 24 hours, the product solution was cooled, and extracted with dichloromethane several times. The extracts obtained were combined, washed with water, and the solvent was removed under reduced pressure. The crude product thus obtained was washed with THF and removed by filtration. The products represented by the structural formulas (2) and (3) were obtained. The structural formula was confirmed by the following results. The yield of the obtained product was 89%. The properties were as follows. mp228-230 ° C; mass
spectrum, m / e 554 (M +). Ana
l. Calcd for C33H31NO7Na:
C, 68.74; H, 5.42; N, 2.43. Fou
nd: C, 68.78: H, 5.64; N, 2.7.
4.1 H-NMR (Compound represented by Structural Formula 2) (CD
Cl3) δ 2.94 (3H, s), 3.18, 4.0
6, (each 2H, d, J = 12.7 Hz), 3.
74 (13H, br s), 6.40-8.02 (10
H, m), 9.51 (1H, s), 1H-NMR (compound represented by Structural Formula 3) (CDCl3) δ 3.84 (1
2H, s), 3.29, 4.39 (each 4H,
d, J = 13.7 Hz), 6.58-8.21 (10
H, m), 9.54 (1H, s). Thus, 5-formyl-17-nitro-25,5
26,27,28-Tetramethoxycalix [4] arene (cone type compound) and (partially cone type) could be obtained.

[Chemical formula 28] (2)

[Chemical Formula 29] (3)

[0016]

According to the present invention, 5-formyl-17-
When nitro-25,27-dimethoxycalix [4] arene is used as a raw material and treated with tetraethylene glycol ditosylate, it has a formyl group and a nitro group on the upper side. 5-formyl-17-nitro25,27-dimethoxycalix [4] Allene-crown-5 (cone type) is obtained, and similarly, 5-formyl-17-nitro2 having a formyl group and a nitro group at a specific site.
5,27-dimethoxycalix [4] arene 26,2
When 8-diol is treated with methyl nitrile and alkali,
5-formyl-having a formyl group and a nitro group on the upper side
17-nitro 25,26,27,28-tetratoxicalix [4] arene (cone type) and (partially cone type) can be obtained. The compound obtained in the present invention is extremely useful as a precursor in the synthesis of, for example, a charge transfer device, porphyrin-calixarene-quinone conjugate, and further, by encapsulating a metal cation in a calixarene hole, a steric structure is obtained. It is a remarkable compound that can change its structure arbitrarily.

[Brief description of drawings]

FIG. 1 NMR of 5-formyl-17-nitro 25,27-dimethoxycalix [4] arene-crown-5.
It is a figure which shows a spectrum.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Makoto Sato 1-1, Higashi 1-1, Tsukuba City, Ibaraki Prefecture Institute of Industrial Science and Technology (56) References New J. Chem. , Vol. 23, No. 10, p. 977-979 (1999) J. Am. Chem. Soc. , Vol. 117, No. 7, p. 2041-2048 (1995) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07D 323/00 C07C 201/12 C07C 205/44 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. 5-Formyl-17-nitro-25,27-dimethoxycalix [4] arene-crown-5 represented by the following structural formula (1). [Chemical formula 1] (1) 2. 5-Formyl-17-nitro-25,26,27,28-tetramethoxycalix [4] arene (cone type compound) represented by the following structural formula (2). [Chemical 2] (2) 3. 5-Formyl-17-nitro-25,26,27,28-tetramethoxycalix [4] arene (partially corn type compound) represented by the following structural formula (3). [Chemical formula 3] (3) 4. 5-formyl-17-nitro-25,27-dimethoxycalix [4] arene-26,28-diol represented by the following structural formula (4) is added with tetraethylene glycol ditosylate and a base. Let the bottom react,
A method for producing 5-formyl-17-nitro-25,27-dimethoxycalix [4] arene-crown-5 represented by the following structural formula (1). [Chemical 4] (5) [Chemical formula 5] (1) 5. A 5-formyl-17-nitro-25,27-dimethoxycalix [4] arene 26,28-diol represented by the following structural formula (5) is reacted with methyl halide or methyl tosylate in the presence of a base. And 5-formyl-17 represented by the following structural formulas (2) and (3).
-A method for producing nitro 25,26,27,28-tetratoxcalix [4] arene (corn type) and (partly cone type). [Chemical Formula 6] (5) [Chemical 7] (2) [Chemical 8] (3)