JPS61207363A - New fumaramide derivatives and alcohol-based compound separation agents made from them - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [A! TECHNICAL FIELD The present invention relates to a novel compound that can be used to separate alcoholic compounds, particularly various compounds having an alcohol group, and its use.

[Prior Art] Conventionally, the separation and purification of alcohol has mainly been carried out by distillation, and since dialcohols have a high boiling point, vacuum distillation is necessary. Separation and purification of substances required a large amount of energy.

On the other hand, the present inventors discovered that a specific compound (host compound) is a specific molecule (guest molecule), starting from the phenomenon of crystallizing solvents.
As a result of research on host-guest complexes or inclusion complexes made by incorporating 1, for example, 8. lO-dihydroxy-8,IO-diphenyl-8,10-dihydroanthracene, 2,5-bis(2,todimethylphenyl)
We have discovered that hydroquinone, 2,5-di(4-chlorophenyl)hydroquinone, etc. have excellent inclusion functions for alcohols (Chemistry Lett
ers (The Chemical 5ociety
of Japan), pp, 1521-1524; Chemical Equipment, August 1984 issue, pp. 35-43).

[Problems to be Solved by the Invention] It is known that the compound of item 1U has an inclusion function for monoalcohols such as methanol and ethanol, as well as dialcohols such as ethylene glycol. The present inventors further continued their search for host compounds useful for the separation and purification of dialcohols, and as a result, they discovered a novel host compound for use in the present invention.

[Means for solving the problems] The novel compound provided as a host compound by the present invention is represented by the following formula: N,N,N',N'-tetracyclohexyl-fumaramide (hereinafter referred to as compound (I)). ) and its derivatives.

This compound (I) is obtained by reacting dicyclohexylamine and fumaric acid chloride using a benzene solvent, filtering the generated dicyclohexylamine hydrochloride, and obtaining +1! The solvent benzene is distilled off from the liquid, and the residue is recrystallized from methanol. The obtained crystal is a mixture of the above compound and methanol.
:It is an inclusion compound of 2, and when it is heated, methanol is expelled.

An amorphous powder of the compound of the present invention is obtained.

Compound ('I) has a melting point of 208-208°C,
Its infrared absorption spectrum is as shown in FIG.

Derivatives of the above compounds can be obtained by using dicyclohexylamine as a raw material having an alkyl group or other side chain in the cyclohexyl group.

Compounds (ri) not only have the ability to include various saturated or unsaturated monoalcohols or dialcohols, but also have the ability to form complexes with polyfunctional compounds having alcohol groups as guest molecules. Since the obtained clathrate compound generally has low solubility in water, it can be precipitated as a crystal from a solution.The obtained crystal is subjected to solid-liquid separation, and after washing and drying, the alcohol is separated by heating or solvent extraction. The recovered alcohol has extremely high purity, and the solid after separation can be reused as compound (1).The heating required to recover the silcols from the clathrate compound is recovered once. When the boiling point of the narcol compound to be used is high, the reaction is carried out under reduced pressure. 'The alcohols separated and produced by the compound (1) of the present invention include methanol, ethanol, propatool, allyl alcohol,
Propargyl alcohol, etc., and examples of dialcohols include ethylene glycol, diethylene glycol, 1.
4-butanediol, 1,4-butynediol (cis
-, trans-), 1.4-butynediol, 1.
These include 8-hexanediol and 1.8-octanediol. As a polyfunctional compound having an alcohol group,
Glycolic acid, 3-hydroxyprobiononitrile, etc. can be mentioned.

Although the mechanism by which compound (I) forms a clathrate compound with alcohols is not necessarily clear, it is thought that the hydroxyl group of the alcohol forms a clathrate compound with compound (1) through hydrogen bonding. Therefore, in addition to alcohol compounds, guest compounds that form clathrate compounds can be considered, and π-containing compounds and carboxylic acids 1, such as acetic acid, can be separated and purified using the compound ([).

There is no particular limitation on the concentration of the alcohol in the solution separated and purified by the present invention, but it is usually 1$ or more, preferably 20
% or more. Although an aqueous solution is used as the solution, any solvent can be used as long as the resulting clathrate compound can be separated by crystallization or other means.1For example, when dialcohol is the target, monoalcohol or monoalcohol may be used depending on the type of dialcohol. A solution of can also be used.

To prepare a clathrate compound using compound (I), compound (1) may be simply added to a solution of alcohol, but
By dissolving or melting the material by heating as necessary, the clathrate compound can be efficiently produced.

Further, the compound (D) can also be used by dissolving it in a solvent such as ether.

[Function] Compound (1) generally has good stability as a complex with an alcohol, and there is little or very little loss of the clathrated alcohol even when the resulting complex is dried. Therefore 1
By using the compound (1) of the present invention, a target alcohol compound can be separated and recovered from a solution with high purity and high yield.

Furthermore, the inclusion ability of the compound (1) of the present invention has selectivity with respect to stereoisomerism, and can be utilized for separation between the cis type and the trans type.

[Example] Example 1 773 g of dicyclohexylamine was placed in an Erlenmeyer flask,
Add benzene 1001 to this. Slowly drop 15.3 g of fumaric acid chloride from the top using a biurette.
In order to prevent exothermic temperature rise, the reaction mixture is externally cooled with water or water, and stirring is continued while keeping the mixture at about room temperature. When the addition is completed, the reaction is completed and dicyclohexylamine hydrochloride is precipitated.

The precipitate is filtered and washed with a small amount of benzene, and the filtrate and washings are combined and distilled under heat to expel the benzene. When the obtained residue is recrystallized from methanol, the compound (I
) and methanol are obtained as colorless prismatic crystals. The crystals were heated to drive out methanol, yielding 40 g (yield: 951) of Compound (1) as an amorphous powder.

Examples of separation of various guest compounds using Compound (I) as a host compound are shown below, but since the compounds used are small, there is a large loss in processing, and yields etc. are not necessarily accurate. , is considered to be under-required.

Example 2 2.0 g of compound (I) prepared above and 30 wt%
The mixture was heated and dissolved in 0.73 g of propargyl alcohol containing water and 3 ml of total n-butanol and allowed to stand at room temperature for 1 hour to precipitate 1.45 g of colorless prismatic crystals. Although this crystal did not show a clear melting point, it showed a small infrared absorption spectrum as shown in Figure 2. By heating it to 150°C, 0.27 g of propargyl alcohol was obtained, and compound (I) and propagyl alcohol were obtained. It was a 1=2 clathrate of gyl alcohol.

Example 3 Compound (I) 2.0 g to 30 wt $ (7) 0.513 g of 2-butyne-1,4-diol containing wood and n-
When heated and dissolved in butanol 51 and left at room temperature for 2 hours, compound (I) and 2-butyne-1,4-diol (1=
2.1 g of colorless prismatic crystals of the l-clathrate compound were obtained. The melting point of this crystal is 176 to 178°C, and its infrared absorption spectrum is as shown in the fS3 diagram.

By heating this crystal to 200°C under reduced pressure of 25 mm 1 g, 0.13 g of 2-butyne-1,4-diol was obtained.
was recovered.

Example 4 1.4 containing 2.0 g of compound (I) and 30 wt% water
When 0.59 g of -butanediol was heated and dissolved in 51 n-butanol and left at room temperature for 2 hours, 1.99 g of an l=l clathrate of compound (I) and n-butanediol was precipitated. This is a colorless prismatic crystal with a melting point of 183-166°C. Figure 4 shows the infrared absorption spectrum.

1.9111 g of this crystal was heated for 20 minutes under reduced pressure of 25 mmHg.
Heating to 0°C yielded 0.27 g of 1,4-butanediol.

Example 5 2- containing 2.0 g of compound (1) and 30% #t% of water
Butene-1,4-diol (cis and tran
Compound (I) and t
1.86 g of l=l clathrate of rams-2-butene-1,4-diol was precipitated. This product was colorless prismatic crystals with a melting point of tet~169°C. When the separated crystals are heated to 200℃ at 25++v+Hg,
trans-2-butene-1,4-diol 0.28g
was gotten.

Example 6 When 2.0 g of compound (1) and 0.20 g of ethylene glycol containing 30 wt$ of water were heated and dissolved in n-butanol 31 and left at room temperature for 1 hour, compound (1) and 2 of ethylene glycol were dissolved. = Colorless needle-like crystals of l clathrate compound 1
．． 80 g was obtained. Although this crystal did not show a clear melting point, it was heated to 150° C. under reduced pressure of 25 s) of Ig to produce 0.0% ethylene glycol. 1Og was recovered and t-0, (2.0g of Example Huich compound (1') and 0.34g of diethylene glycol containing 30% of water were mixed with n-butanol 3ω.
1 and stirred at room temperature for 1 hour, the compound m
and diethylene glycol) 2:l clathrate compound 1.94
g is the precipitation 1-. This substance is a colorless prismatic crystal.
It showed a melting point of 151-155°C. II! ! The collected crystal was heated to 25mmHg+:? ) Heating to 200° C. under reduced pressure yielded 0.09 g of diethylene glycol.

Indeed @8-12 Compound (I) is a host and 1. Table 1 shows the reaction conditions and the properties of the complexes for each of the inclusion complexes with various Gess I compounds obtained. All complex crystals! It was the color.

4! Figure 1 shows the infrared absorption spectrum of N, N, N', N'-tetracyclohexyl-thujaramide of the present invention. The infrared absorption spectra of various clathrate compounds obtained in the above are shown.

Claims (6)

[Claims] (1) N,N,N',N'-tetracyclohexyl-fumaramide and its derivatives represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. (2) An alcoholic compound separating agent made of N,N,N',N'-tetracyclohexyl-fumaramide and its derivatives, represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼. (3) The alcohol compound separating agent according to claim 2, wherein the alcohol compound to be separated is a monoalcohol. (4) The alcohol compound separating agent according to claim 2, wherein the alcohol compound to be separated is a dialcohol. (5) The alcohol compound separating agent according to claim 2, wherein the alcohol compound to be separated is a polyfunctional group compound having an alcohol group. (6) Carboxylic acid separating agent made of N,N,N',N'-tetracyclohexyl-fumaramide and its derivatives, represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼.