JPS61233653A - Diacetylene diol molecular inclusion complex - Google Patents

Abstract

NEW MATERIAL:A molecular inclusion complex consisting of one molecule 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol expressed by formula I and two molecules dimethylacetamide. USE:Useful for preserving dimethylacetamide (DMA) stably in the solid state. PREPARATION:Diacetylenediol expressed by formula I is reacted with dimethylacetamide (DMA) expressed by formula II to give the aimed compound assumed as formula III. The reaction is carried out by dissolving the compound expressed by formula I in the dimethylacetamide in a molar excess amount of twice or more or adding the diacetylenediol to a mixture solution of the dimethylacetamide with water. The aimed compound can be utilized for recovering the dimethylacetamide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1.1.6.6-titraphenylhexar2.
This invention relates to a novel molecular inclusion complex of 4-diyne-1,6-diol (hereinafter abbreviated as diacetylene diol) and dimethylacetamide, which is an excellent polar solvent.

It is known that diacetylene diol can be used to create molecular inclusion compounds with various solvents and low-molecular organic compounds, and that this can be used for the separation of stereoisomers, such as the separation of optically active forms from racemates (Journal of the Chemical Society of Japan). Bian 2, P2S5.1
986).

The present inventors focused on the unique behavior of diacetylene diol and studied its complex formation, and found that one molecule of diacetylene diol and two molecules of dimethylacetamide form a molecular inclusion complex.

The present invention is based on this knowledge, and consists of one molecule of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol and two dimethylacetamide molecules represented by the following formula.
It is a molecular inclusion complex consisting of molecules.

The molecular clathrate compound of the present invention can be obtained by reacting diacetylene diol of the following formula with dimethylacetamide represented by the following formula.

Diacetylene diol (1) is reacted with penzophenone and acetylene sodium, and the resulting compound represented by the following formula is dissolved in acetone containing pyridine and cuprous chloride, and oxygen is blown in to perform a coupling reaction. It can be obtained by

The precipitated crystals are recrystallized from benzene, and the resulting white powder crystals are purified by heating under reduced pressure to evaporate acetone and benzene.

When producing the molecular inclusion complex of the present invention, diacetylene diol is dissolved in dimethylacetamide in an excess of 2 times the mole or more, or diacetylene diol is added to a mixture of dimethylacetamide and water and reacted. let The reaction proceeds at room temperature, but the reaction may be accelerated if necessary by heating. After the reaction is completed, the reaction mixture is cooled, the precipitate is collected, washed with water, and then dried to obtain the target compound.

This compound has a clear melting point around 125° C., and elemental analysis confirms that the compounds of formulas I and (2) form a complex in a ratio of 1=2.

Also, according to the infrared absorption spectrum, the absorption peak of diacetylene diol 10H is about 55607? Since m-' has moved to about 318014'ff+-' in the target compound, the carbonyl group of dimethylacetamide is hydrogenated to the two 10H hydrogens of diacetylene diol as shown in the following formula. It is presumed that they are connected.

The molecular inclusion complex of the present invention is useful for stably preserving dimethylacetamide in a solid state.

Furthermore, by adding diacetylene diol to a mixture of water and dimethylacetamide, dimethylacetamide can be separated as the crystalline molecular clathrate of the present invention, and when this molecular clathrate is heated under reduced pressure, dimethylacetamide can be easily separated. This compound can also be used for the recovery of dimethylacetamide.

4 Example 1 2.875 g (6,94
After heating and dissolving X 10-3 mol) in 10 ml of dimethylacetamide, the solution was cooled to room temperature and left for 4 hours. The precipitated crystals were collected, washed with water, and then dried under reduced pressure at room temperature to obtain 3.806 g of the target compound. The melting point of this compound was measured by differential calorimetry (DTA) and was found to be 125°C. Note that the melting point of diacetylene diol (I) is 148 to 149°C. Further, the elemental analysis values of diacetylene diol (I) and the target compound are as follows.

Diacetylenedio-/I/:C as C3oH2202
HO Theoretical value 86.93 5.35 7.72 Actual value 87
．． 53 5.21 7.71 Target compound: csoH
2tot・2 (C,H,No) as CI(N
O Theoretical value 77.52 6.85 4.76 10.87
Actual value 77.78 6.85 4.84 10.53
As a result of elemental analysis of the product, the measured value and the theoretical value agree within the error range, indicating that this compound is diacetylene diol 1
It was confirmed that it is a complex consisting of a molecule and two molecules of dimethylacetamide.

Also, since the molecular weight of this compound is 588, its yield is 3.8031588 = 6.46X 10-" moles, and 6.46 X 10-3/6.94 X 10-" =
From 0°96, 96% of diacetylene diol was obtained as the target compound. Diacetylene diol (
The infrared absorption spectra of I) and the target compound measured by the KBr tablet method are shown in FIGS. 1 and 2. 355 in Figure 1
．． The absorption observed at 0cIn' is the absorption of the 10H group of diacetylene diol, and in Figure 2, this absorption peak disappears and a new broad absorption appears at 6180 l-1, and at 1620 cm. 'A sharp absorption, which is assumed to be carbonyl absorption, is seen.

Example 2 1 g of diacetylene diol was placed in 6 [1 ml] of a mixed solution of water/dimethylacetamide at a volume ratio of 1:1, and the mixture was stirred at room temperature all day and night. Next, the precipitate was separated, washed with water, and then dried under reduced pressure at room temperature to obtain 1.2789 white crystalline powder. Although diacetylene diol did not appear to dissolve, the infrared absorption spectrum of the obtained compound showed a spectrum similar to that shown in FIG. 2, confirming that a complex was formed. Furthermore, the results of elemental analysis revealed that the compound had the same composition as the compound obtained in Example 1.

When this compound was heated at 100° C. (3,5 xi Hg vacuum) and the evaporated material was collected in a trap and examined, only dimethylacetamide was obtained.

Moreover, the infrared absorption spectrum of the evaporation residue matched that of FIG. 1, and it was confirmed that this was diacetylene diol.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of diacetylene diol.
FIG. 2 is an infrared absorption spectrum of a molecular clathrate compound obtained from diacetylene diol and dimethylacetamide.

Claims (1)

[Claims] 1,1,6,6-tetraphenylhex-2 represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1)
A molecular inclusion complex consisting of one molecule of ,4-diyne-1,6-diol and two molecules of dimethylacetamide.