JPH0713044B2 - Novel calixarene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel calixarene derivative and a method for producing the same. More specifically, the present invention has the general formula (I) (Where n is the number of aromatic rings forming the skeleton of 4 to 8, M is hydrogen, sodium ion), p-nitro-calix [n] arene, its sodium salt, and its production method. .

Recently, Gutsche et al. "Calyxalene" (a compound of the general formula (I) in which M is hydrogen and the -NO ₂ group is replaced by hydrogen. Its shape resembles that of a cup (Calix) and its aroma. Calixar because it is a family compound (arene)
We have reported a series of cyclic host molecules called ene (eg CDGutsche, Acc.Ch).
em.Res., 16 , 161 (1983)).

However, p as a useful intermediate for synthesizing calixarenes (referred to as calix [n] arene in the present specification for the sake of convenience: n is the number of aromatic rings serving as a skeleton) has a catalytic ability similar to that of enzyme. -Nitro-calix [n] arene cannot be synthesized / separated by direct nitration of calix [n] arene (e.g.
Zinke, R.Ott, andF.H.Garrana, Monatsh.Chem., 89 , 135 (1
958)). In addition, Gucche's recent book (CD Gutsche, “H
ost Guest Complex Chemistry / Macrocycles ", ed by FV
ogtle and E. Weber, Springer-Verlag, Berlin, 1985, p37
Also in 5.), there is a description that p-nitro-calix [n] arene cannot be obtained by direct nitration of calix [n] arene. The present inventors also conducted research on synthesis, separation, and purification by making full use of various methods, but in direct nitration of calixarene itself in an organic solvent or sulfuric acid, many substances other than the target substance It was impossible to generate and separate. Under these circumstances, the present invention has been completed as a result of separately researching an efficient method for synthesizing p-nitro-calix [n] arene and its sodium salt.

That is, 1) general formula (I) P-nitro-calix [n] arene (where n is the number of aromatic rings forming the skeleton of 4 to 8 and M is hydrogen or sodium ion) 2) concentration 90% or more, preferably 95% or more Of calix [n] arene-p-sulfonic acid generated by reacting calix [n] arene in concentrated sulfuric acid, suspending, heating to 80 ° C or higher, preferably 90 ° C or higher, and removing the reaction product. Dilute with sulfuric acid so that the concentration of sulfuric acid is 30-70%, then cool.
A method for producing p-nitro-calix [n] arene represented by the above general formula (I), characterized in that nitric acid or a nitrate (sodium, potassium) is added to substitute the sulfo group for a nitro group.

3) Sulfuric acid concentration as a reaction solvent is 30 to 70%, preferably 45 to
In the range of 50%, 1 to 1.2 molar ratio of nitric acid or nitrate per phenol unit of calix [n] arene-p-sulfonic acid is used, and the reaction temperature is 10 ° C or lower, preferably 5 ° C or lower to convert the sulfo group to the nitro group. The production method described in 2) above, which comprises performing a substitution reaction.

4) The nitration reaction product was diluted with water, separated and washed with water to obtain crude p-nitro-calix [n] arene, which was dissolved in dilute aqueous sodium hydroxide solution, decolorized with activated carbon and filtered,
Add about 5% by weight of solution of sodium hydroxide to the filtrate,
Crystals of high-purity sodium salt of p-nitro-calix [n] arene are deposited, and the crystals are filtered, washed with brine and dried to obtain a sodium salt of p-nitro-calix [n] arene. Next, the sodium salt of p-nitro-calix [n] arene is dissolved in water, the solution is acidified with hydrochloric acid or sulfuric acid, and the precipitated crystals are filtered, washed with water,
The above-mentioned 2), characterized in that high-purity p-nitro-calix [n] arene crystals are obtained by drying.
3) The manufacturing method described.

Regarding

The calix [n] arene, which is the raw material of the present invention, is synthesized by the known method described in the above-mentioned literature. That is,
p-tert-Butylphenol, formaldehyde, and sodium hydroxide are heated under various conditions, and p-tert-butylcalix [n] arene obtained from the obtained condensate is heated with anhydrous aluminum chloride in toluene. Obtained by debutylation. These calix [n] arenes were further purified, sulfonated by the method described above and used for the present invention. The present invention will be described in more detail below.

The concentration of nitric acid or nitrate used in the substitution reaction is not particularly limited, but 1 to 1.2 mol may be used per phenol unit of p-sulfo-calix [n] arene,
The use of more nitric acid or nitrate increases side reactions such as oxidation and causes a decrease in yield. Further, in precipitating crystals of sodium salt of p-nitro-calix [n] arene, after decolorization and filtration with activated carbon, sodium hydroxide in an amount of about 5% by weight of the solution was added to p-nitro-calix [n]. ] The sodium salt of allene is precipitated,
It is not possible to obtain high-purity sodium salt crystals of p-nitro-calix [n] arene by increasing the sodium hydroxide concentration to a higher concentration or by salting out using salt or the like. Therefore, p-nitro-calix [n] arene, which is the object of the present invention, cannot be obtained with high purity and high yield, which is not a preferable method. Further, when a higher-purity p-nitrocalix [n] arene is required, it is dissolved in an alkaline solution and purified with activated carbon.
Pure sodium p-nitro-was added by salting out sodium salt by adding t% by weight of caustic soda, filtering and washing with brine.
The sodium salt of calix [n] arene can be obtained. Further, this sodium salt is dissolved in water and subjected to acid precipitation to easily obtain highly pure p-nitro-calix [n].
You can get Allen.

In order to specifically describe the present invention, examples will be given below to further specifically describe the present invention.

Example 1 5.0 g of calix [6] arene was added to 50 ml of concentrated sulfuric acid to give 80
The heat sulphonation reaction was carried out at 4 ° C. for 4 hours, post-cooling and the reaction mixture was diluted with 90 ml of cold water.

Next, 5.5 g of 61% nitric acid was added, and the reaction was carried out for 10 hours while maintaining the inside of the reaction system at 0 to 5 ° C. to complete the substitution reaction. After the reaction, the reaction mixture was diluted with water, and the generated crystals were separated, washed with water and dried to obtain 2.5 g of crude p-nitro-calix-6-arene.
35% yield based on calix [6] arene.

Example 2 Crude p-nitro-calix [6] arene obtained in Example 1
5.0 g was dissolved by heating in 300 ml of water and 1.5 g of sodium hydroxide, and 2 g of activated carbon was added and filtered. 15 g (5% by weight of the solution amount) of sodium hydroxide was added to the filtrate to precipitate a pure hexasodium salt. Then, filtration, washing with brine and drying were performed to obtain 4.1 g of purified hexa sodium salt of p-nitro-calix [6] arene. This product contained common salt and water, and as a result of analysis, the purity of p-nitro-calix [6] arene as a hexasodium salt was 63%. (Yield 45%, relative to crude p-nitro-calix [6] arene) Example 3 4.0 g of crude p-nitro-calix [6] arene hexasodium salt (purity 63%) obtained in Example 2 was added to water. 1 ml of concentrated hydrochloric acid was added while heating to dissolve to 100 m, and the precipitated crystals were filtered, washed with water and dried to obtain 2.1 g of pure p-nitro-calix [6] arene.

(Yield 96%, hexasodium salt of p-nitro-calix [6] arene) Examples 4 to 7 p-nitro-synthesized according to the methods of Examples 1, 2 and 3.
The following analyzes were performed for each of the calix [n] allenes. The results are shown in the table.

Claims (4)

[Claims] 1. A general formula (I) P-nitro-calix [n] arene represented by (In the above formula, n represents the number of aromatic rings forming the skeleton of 4 to 8, and M represents hydrogen or sodium ion.) 2. A calix [n] arene-p-sulfonic acid formed by suspending calix [n] arene in concentrated sulfuric acid having a concentration of 90% or more and heating the mixture to 80 ° C. or higher for reaction. The sulfuric acid concentration of the reaction product is 30 to 70% without taking it out.
P-nitro represented by the above general formula (I), wherein the sulfo group is replaced with a nitro group by adding nitric acid or a nitrate salt (sodium, potassium) under cold temperature. -A method for producing calix [n] arene. 3. A nitric acid or a nitrate of 1 to 1. per 1 phenol unit of calix [n] arene-p-sulfonic acid in a sulfuric acid concentration of 30 to 70%, preferably 45 to 50% as a reaction solvent.
2 molar ratio is used, the reaction temperature is below 10 ℃, preferably 5 ℃
The p-nitro-calix [n] according to claim 2, wherein the substitution reaction of the sulfo group with the nitro group is carried out below.
Allen manufacturing method. 4. A crude p-nitro-calix [n] arene obtained by diluting the nitration reaction product with water, separating and washing with water is dissolved in a dilute aqueous sodium hydroxide solution, decolorized and filtered with activated carbon, and then the filtrate. To the solution was added sodium hydroxide in an amount of about 5% by weight to precipitate crystals of sodium salt of p-nitro-calix [n] arene, and the crystals were filtered, washed with brine and dried to obtain p-. Nitro-Calix [n]
The sodium salt of allene is obtained, then the sodium salt of p-nitro-calix [n] arene is dissolved in water, the solution is acidified with hydrochloric acid or sulfuric acid, and the precipitated crystals are filtered, washed with water and dried to give p- Nitro-Calix [n]
Claims 2 or 3 to obtain crystals of allene
The method for producing p-nitro-calix [n] arene according to the item 1.