JPH0456822B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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 alcohols has mainly relied on distillation, and since dialcohols have a high boiling point, vacuum distillation is necessary. The energy consumption for separation and purification was large.

On the other hand, the present inventors have conducted research on host-guest complexes or clathrate complexes, which are formed by a specific compound (host compound) incorporating a specific molecule (guest molecule), based on the physique of crystallization solvents. As a result, for example, 9,10-dihydroxy-9,10-diphenyl9,10-dihydroanthracene, 2,5-
We discovered that bis-(2,4-dimethylphenyl)hydroquinone, 2,5-di(4-chlorophenyl)hydroquinone, etc. have excellent inclusion functions 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] The above compounds are known to have an inclusion function for monoalcohols such as methanol and ethanol, as well as dialcohols such as ethylene glycol. As a result of their continued search for host compounds useful for the separation and purification of dialcohols, they discovered a new 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 has the following formula: N,N,N',N'-tetracyclohexyl-fumaramide {hereinafter referred to as compound ()} and its derivatives, represented by:

This compound () is obtained by reacting dicyclohexylamine and fumaric acid chloride using a benzene solvent, filtering the resulting dicyclohexylamine hydrochloride, and recrystallizing the residue from methanol after distilling off the solvent benzene from the filtrate. The obtained crystals are a 1:2 clathrate of the above compound and methanol, and when this is heated, methanol is expelled and an amorphous powder of the compound of the present invention is obtained.

This compound () has a melting point of 206-208℃,
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.

Compound () not only has the ability to include various saturated or unsaturated monoalcohols or dialcohols, but also has the ability to include polyfunctional compounds having alcohol groups to form complexes as guest molecules. . Since the resulting clathrate compound generally has low solubility in water, it can be precipitated as crystals from a solution. After solid-liquid separation of the obtained crystals, washing and drying, the alcohol can be separated by heating or solvent extraction. The separated and recovered alcohol has extremely high purity, and the solid after separation can be reused as a compound (). Heating for recovering alcohols from clathrate compounds is performed under reduced pressure when the alcohol compound to be recovered has a high boiling point.

The alcohols separated and produced by the compound () of the present invention include methanol, ethanol, propanol, allyl alcohol, propargyl alcohol, etc. as monoalcohols, and ethylene glycol, diethylene glycol, 1,4 -butanediol, 1,4
-Butenediol (cis-, trans-) 1,4-butynediol, 1,6-hexanediol, 1,
8-octanediol and the like. Examples of polyfunctional compounds having alcohol groups include glycolic acid,
Examples include 3-hydroxypropiononitrile.

Although the mechanism by which compound ( ) 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 ( ) through hydrogen bonding. Therefore,
In addition to alcohol compounds, guest compounds that form clathrate compounds can be considered, and in fact, carboxylic acids, such as acetic acid, can be separated and purified using 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 it is 20% or more. An aqueous solution is used as the solution, but any solvent can be used as long as the resulting clathrate can be separated by crystallization or other means. For example, when dialcohol is the target,
Depending on the type of dialcohol, a monoalcohol solution may also be used.

To make an inclusion compound using compound (),
Although the compound () may be simply added to a solution of alcohol, the clathrate compound can be efficiently produced by dissolving or melting it by heating, if necessary. Moreover, the compound () can also be used by dissolving it in a solvent such as ether.

[Function] Compound () generally has good stability of alcohols and their complexes, and there is little or very little loss of clathrated alcohols even when the resulting complex is dried. Therefore, by using the compound () of the present invention, it is possible to separate and recover the target alcohol compound from a solution with high purity and high yield.

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

[Examples] Example 1 Production of N,N,N',N'-tetracyclohexyl-fumaramide {compound ()} 73 g of dicyclohexylamine was placed in an Erlenmeyer flask, and 100 ml of benzene was added thereto. 15.3 g of fumaric acid chloride is slowly added dropwise from the top using a biuret, and in order to prevent heat generation, the mixture is cooled with water or ice from the outside, and stirring is continued while keeping the temperature at approximately room temperature. When the dropwise addition is completed, the reaction is completed and dicyclohexylamine hydrochloride is precipitated.

Filter the precipitate, wash with a small amount of benzene,
The filtrate and washing liquid are combined and heated and distilled to drive out the benzene. When the obtained residue is recrystallized from methanol, a 1:2 clathrate compound of compound () and methanol is obtained as colorless prismatic crystals. The crystals were heated to drive out methanol, yielding 40 g (yield 95%) of compound (2) as an amorphous powder.

Examples of separation of various guest compounds using compound () as a host compound are shown below, but since the amount of the compound used is small, there is a large loss during processing, and the yield etc. cannot necessarily be said to be accurate. This is considered to be what is required.

Example 2 2.0 g of the above-produced compound () and 30 wt%
Propargyl alcohol containing 0.73g of water and n-
When the mixture was heated and dissolved in 3 ml of butanol and left at room temperature for 1 hour, 1.45 g of colorless prismatic crystals were precipitated.
Although this crystal did not show a clear melting point, it showed an infrared absorption spectrum as shown in Figure 2.
By heating to 150°C, 0.27 g of propargyl alcohol was obtained, which was a 1:2 clathrate of compound () and propargyl alcohol.

Example 3 2.0 g of compound () and 0.56 g of 2-butyne-1,4-diol containing 30 wt% water were heated and dissolved in 5 ml of n-butanol and left at room temperature for 2 hours.
2.1 g of colorless prismatic crystals of a 1:1 clathrate compound of compound (2) and 2-butyne-1,4-diol were obtained. The melting point of this crystal is 176-178°C, and its infrared absorption spectrum is as shown in Figure 3.

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

Example 4 1,4 containing 2.0 g of compound () and 30 wt% water
-butanediol 0.59g and n-butanol 5ml
When dissolved by heating and left at room temperature for 2 hours, a 1:1 clathrate compound of compound () and n-butanediol is formed.
1.99g was precipitated. This is a colorless prismatic crystal with a melting point of 163-166°C. Figure 4 shows the infrared absorption spectrum.

1.99 g of this crystal was heated to 200° C. under a reduced pressure of 25 mmHg to obtain 0.27 g of 1,4-butanediol.

Example 5 When 2.0 g of compound () and 0.57 g of 2-butene-1,4-diol (mixture of cis and trans types) containing 30 wt% water were heated and dissolved in 5 ml of n-butanol and left at room temperature for 2 hours. , compound () and
1:1 of trans-2-butene-1,4-diol
1.86 g of clathrate compound was precipitated. This product was colorless prismatic crystals with a melting point of 161-169°C.
When the filtered crystals are heated to 200℃ at 25mmHg,
0.28 g of trans-2-butene-1,4-diol was obtained.

Example 6 2.0 g of compound () and 0.20 g of ethylene glycol containing 30 wt% water are heated and dissolved in 3 ml of n-butanol and left at room temperature for 1 hour to form a 2:1 clathrate compound of compound () and ethylene glycol. 1.80 g of colorless needle-like crystals were obtained. This crystal did not show a clear melting point, but under a reduced pressure of 25 mmHg,
By heating to 150°C, 0.10 g of ethylene glycol was recovered.

Example 7 When 2.0 g of compound () and 0.34 g of diethylene glycol containing 30 wt% water are heated and dissolved in 3 ml of n-butanol and left at room temperature for 1 hour, 1.94 g of a 2:1 clathrate compound of compound () and diethylene glycol is obtained. was precipitated. This product was colorless prismatic crystals with a melting point of 151-155°C. The crystals collected by filtration were heated to 200° C. under a reduced pressure of 25 mmHg to obtain 0.09 g of diethylene glycol.

Examples 8 to 12 Table 1 shows the reaction conditions and properties of the clathrate complexes with various guest compounds obtained using Compound () as a host. All complex crystals were colorless.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of N,N,N',N'-tetracyclohexyl-fumaramide of the present invention. Figures 2 to 4 are obtained by the present invention, respectively.

【table】

[Table] *The molar ratio of the inclusion complex indicates the host:guest molar ratio.
The figure shows the infrared absorption spectra of various clathrate compounds.

Claims (1)

[Claims] Linear formula N,N,N',N'-tetracyclohexyl-fumaramide and derivatives thereof, represented by: Quadratic equation An alcoholic compound separating agent comprising N,N,N',N'-tetracyclohexyl-fumaramide and its derivatives, represented by: 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 compound having an alcohol group. 6th order equation A carboxylic acid separating agent consisting of N,N,N',N'-tetracyclohexyl-fumaramide and its derivatives, represented by: