JPH0477741B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel benzene polycarboxylic acid polyamide compound, specifically, N, N, N', N',
N″,N″-hexacyclohexyl-1,3,5-
Benzenetricarboxylic acid triamide and N,
It relates to N,N',N',N'',N'',N,N-octacyclohexyl-1,2,4,5-benzenetetracarboxylic acid tetraamide. The present compound can be used as a host compound to form a packaging complex with various solvent compounds including alcohols and phenols as guest compounds, and can be used for the separation and purification of these compounds. [Prior Art] Originating from the phenomenon of crystallizing solvents, the present inventors conducted research on host-guest complexes or inclusion complexes formed by a specific compound (host compound) incorporating a specific molecule (guest molecule). As a result, for example, 9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene, 2,5-bis(2,4-dimethylphenyl)hydroquinone, 2,
We discovered that 5-di(4-chlorophenyl)hydroquinone and the like have an excellent inclusion function for alcohols {Chemistry Letters (The
Chemical Society of Japan), pp.1521-1524;
Chemical Equipment, September 1984 issue, pp. 35-43}. [Problems to be Solved by the Invention] On the other hand, the present inventors have previously discovered that diacetylene diols incorporate various guest compounds to form stable crystalline complexes.
1,1,6,6-tetraphenylhex-2,4
Diyne-1,6-diol and DMF form a 1:2 complex. Based on this, we discovered the possibility of obtaining a host compound that incorporates an alcohol-based compound by molecularly designing a host compound having an amide bond. [Means for solving the problem] As a result of various searches in pursuit of the above-mentioned possibilities, the present inventors found that an amide derivative of a specific symmetrical benzene polycarboxylic acid is included in a wide range of compounds. It was discovered that it has the ability. That is, the novel compound provided as a host compound by the present invention has the following formula: (Here, n is 3 or 4) A novel benzene polycarboxylic acid polyamide represented by N, N, N', N',
N″,N″-hexacyclohexyl-1,3,5-
Benzenetricarboxylic acid triamide (first compound) and N, N, N′, N′, N″, N″, N, N
-octacyclohexyl-1,2,4,5-benzenetetracarboxylic acid tetraamide (second compound). These compounds are produced by reacting dicyclohexylamine with the corresponding benzene polycarboxylic acid chloride using a benzene solvent, separating the by-product amine hydrochloride, and recrystallizing it with methanol. An inclusion complex is obtained, which is heated to drive off the methanol and yield a powder of the compound of the invention. It has been found that the compound of the present invention has an inclusion ability that incorporates not only alcohol compounds but also a wide variety of guests including aromatic hydrocarbons.
The resulting inclusion complex can be precipitated as crystals. The guest can be extracted from the resulting complex using a distillation method, a column chromatography method, a substitution method with another guest, a separation elution method using an acid or a base, etc., depending on the physical and chemical properties of the guest molecules. When the vapor pressure of the guest is relatively low, it is convenient to carry out heating distillation. The separated and recovered guest compound has high purity, and the separated solid can be reused as a host compound. Heating for recovering the guest compound from the inclusion complex is performed under reduced pressure if the guest compound to be recovered has a high boiling point. There are a wide variety of guest compounds that form inclusion complexes with the compounds of the present invention, such as methanol,
Monoalcohols such as ethanol, phenol, cresols such as cresol, aromatic compounds such as benzene and toluene, organic acids and their esters such as acetic acid, benzoic acid, and ethyl benzoate, and naphthalene. Examples include polycyclic aromatic compounds such as methylnaphthalene, and various solvents such as DMF, THF, dioxane, dichloromethane, and trichloroethane. Preparation of clathrate compounds using the compounds of the present invention is carried out simply by contacting the guest compound and the compound of the present invention, and if necessary,
A clathrate compound can be efficiently produced by dissolving or melting it by heating. Further, the compound of the present invention can also be used by dissolving it in a solvent in which the compound does not have inclusion ability. [Function and Effect] Since the compound of the present invention forms a stable complex using various compounds as guest compounds, it can be used to separate and produce these compounds. In addition, there are similar compounds that form a complex and those that do not. For example, isobutanol forms a 1:1 complex with the compound (1) of the present invention, but n
-Butanol does not form a complex, so it can be used to separate the two. [Example] Example 1 Production of N,N,N',N',N'',N''-hexacyclohexyl-1,3,5-benzenetricarboxylic acid triamide (first compound) Trimesic acid and Add phosphorus pentachloride at a molar ratio of 1:3 and mix well. Approximately 80℃
The reaction starts when heated to . After the reaction has almost subsided, the mixture is refluxed for about 2 hours. By vacuum distillation
When POCl ₃ is distilled off, trimesic acid chloride is obtained as a solid. The yield was almost 100%. Into a three-necked flask equipped with a Dimroth condenser and dropping funnel, 6 moles of dicyclohexylamine dissolved in an equal amount of benzene were added, and 1 mole of the trimesic acid chloride obtained above was dissolved in an equal amount of benzene. It is placed in a dropping funnel, and the Dimroth cooler and dropping funnel have a desiccant installed in the opening to shut out moisture from the outside air. While cooling the three-necked flask with ice, add the trimesic acid chloride solution little by little, and occasionally shake the flask by hand to stir the contents. When the addition is complete, shake well and leave at room temperature overnight. The precipitated amine hydrochloride is filtered and washed with a small amount of benzene, and the filtrate and washing liquid are combined and heated and distilled to expel the benzene. When the obtained residue is recrystallized from methanol, it is purified as a 1:2 complex with methanol. This complex was heated to drive out methanol, yielding an amorphous powder of the first compound. The yield was 75%. FIG. 1 shows the infrared absorption spectrum of the methanol complex obtained above, and FIG. 2 shows the infrared absorption spectrum of the first compound obtained by decomposing it. Example 2 N,N,N',N',N'',N'',N,N-octacyclohexyl-1,2,4,5-benzenetetracarboxylic acid tetraamide (second compound)
Production: Place pyromellitic anhydride and phosphorus pentachloride in a molar ratio of 1:2 in an eggplant-shaped flask and shake well. Pyromellitic acid chloride was obtained in a yield of approximately 100% by operating in the same manner as in Example 1. The molar ratio of the obtained pyromellitic acid chloride and dicyclohexylamine was set to 1:8, and Example 1
A second compound was obtained using the same apparatus as above. However, benzene or THF is used as the recrystallization solvent. The yield was 70%. FIG. 3 shows the infrared absorption spectrum of the second compound obtained. Complexes obtained with both compounds of the invention are shown in Table 1. In the table, the symbol "-" indicates that no complex formation was observed.

【table】

【table】

【table】

【table】 [Brief explanation of the drawing]

Figure 1 shows N, N, N', N', N'', N''-
1:2 of hexacyclohexyl-1,3,5-benzenetricarboxylic acid triamide and methanol
Figure 2 shows the infrared absorption spectrum of the complex, N, N, N', N', N'', N''-
It is an infrared absorption spectrum of hexacyclohexyl-1,3,5,-benzenetricarboxylic acid triamide. Figure 3 shows N, N, N', N', N'', N'',
N,N-octacyclohexyl-1,2,
It is an infrared absorption spectrum of 4,5-benzenetetracarboxylic acid tetraamide.

Claims (1)

[Claims] Linear formula (Here, n is 3 or 4) A novel benzene polycarboxylic acid polyamide represented by: 2. The novel benzene polycarboxylic acid polyamide according to claim 1, which is trimesic acid amide where n is 3. 3. The novel benzene polycarboxylic acid polyamide according to claim 1, which is a pyromellitic acid amide in which n is 4.