JPS5812263B2 - Macrocyclic hexaketones and their production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel macrocyclic hexaketone and a method for producing the same. Regarding the manufacturing method.

In recent years, uranyl ions (UO2) have been extracted from seawater, industrial wastewater, etc.
10) Attempts have been made in many fields to remove or recover various types of heavy metal ions, such as copper ions, nickel ions, etc.

In particular, uranyl ions exist in seawater as stable carbonate complexes at about 3.3 ppb, so in order to extract uranyl ions from seawater on an industrial scale, uranyl ions can be easily extracted from carbonate complexes. Moreover, it is necessary to use a material that has the ability to selectively extract other metal ions such as magnesium ions.

The present inventors have conducted repeated research on cyclic compounds having the ability to capture metal ions from the above viewpoint.

As a result, new macrocyclic hexaketones, consisting of six oxygen atoms arranged almost coplanarly toward the inside of the ring at an appropriate distance from the center of the cyclic molecule, are able to transform uranyl from carbonate complexes due to their strong negative charge. We found scales that can easily extract ions and scales that selectively and stably capture uranyl ions as hexadentate ligands.

In addition, in the course of this research, we introduced a conventionally known method (J .Am.Chem.Soc,
, 99, 8366 (1977)), it is difficult to produce a cyclic triketone, but the desired diketone can be produced by reacting a specific diyne compound and/or triyne compound with an acetylene bond at the end with pimeryl chloride. We have discovered that the novel macrocyclic hexaketone described above, which is a cyclic trimer of , can be efficiently produced.

The present invention was completed based on this knowledge.

That is, the present invention is a macrocyclic hexaketone represented by the formula 1.3.9-1
1.l7.l9-hexaoxocyclotetracosane with the formula CH壬C(CH2)5COCH=CCl(CH2)5C
10-chloroheptadec-9-en-8-one-1,16-diyne (β-chloroenone) represented by 3CH
and/or the formula cH3C(CH2)5COC3C(CH2)5C3CH
The above method, characterized in that heptadec-8-one-1,9,16-triin (ynone) represented by: is reacted with pimeryl chloride in the presence of a Lewis acid catalyst, and then the obtained product is hydrolyzed. A method for producing macrocyclic hexaketones is provided.

The macrocyclic hexaketone of the present invention has a structure in which six oxygen atoms are arranged toward the inside of the ring on almost the same plane at a certain distance from the center of the cyclic molecule. The ring size is large enough to allow heavy metal ions to enter the molecule, and the stability of the ring structure is maintained.

Therefore, the macrocyclic hexaketone according to the present invention has an excellent ability to extract and capture uranyl ions from carbonate complexes.

The macrocyclic hexaketone of the present invention resonates as a ketoenol tautomer as follows.

Next, the method of the present invention for producing the above-mentioned macrocyclic hexaketone will be explained.

In the method of the present invention, the aforementioned β-chloroenone and/or ynone is first reacted with pimeryl chloride in the presence of a Lewis acid catalyst.

The raw materials β-chloroenone and ynone may be used alone or in combination.

The reaction conditions are not particularly limited and may be selected as appropriate, but usually a halogen-containing solvent such as methylene chloride, chloroform, dichloroethane, a sulfur-containing solvent such as carbon disulfide, or an aromatic hydrocarbon such as nitrobenzene is used as a solvent.
It may be carried out at room temperature for 5 minutes to 15 hours.

Furthermore, in the method of the present invention, the presence of a Lewis acid catalyst is essential.

This is because in the absence of a catalyst, the reaction will be extremely slow and the decomposition reaction will mainly proceed.

Preferred examples of the Lewis acid used here include tin halides such as stannic chloride, and aluminum halides such as aluminum chloride.

In addition, boron trifluoride, ferric chloride, zinc chloride, titanium tetrachloride, and cupric chloride can also be used.

However, since the product obtained here contains carbon-carbon triple bonds and chlorine atoms, it does not have sufficient ability to trap metal ions.

The process of the invention therefore requires, after carrying out the above-mentioned reaction, ie the reaction of β-chloroenone and/or ynone with pimeryl chloride, to further hydrolyze the product obtained.

Through this hydrolysis, the carbon-chlorine bond and carbon-carbon triple bond in the product become carbonyl groups (enol groups), yielding the desired macrocyclic hexaketone.

Hydrolysis at this time may be carried out by a conventional method using an acid or a base.

The method of the present invention not only produces the above-mentioned macrocyclic hexaketone, but also involves the repeated reaction of the terminal acetylenic hydrocarbon such as the above-mentioned β-chloroenone or ynone with an acid chloride such as pimeryl chloride in multiple stages. It can also be applied to the production of various macrocyclic polyketones.

As mentioned above, the new macrocyclic hexaketone of the present invention has excellent ability to capture metal ions such as uranyl ions, copper ions, and nickel ions. Therefore, by using it, various metal ions, especially uranyl ions, etc. can be removed from dilute aqueous solutions. It can be extracted almost quantitatively and quickly.

Therefore, the above-mentioned novel macrocyclic hexaketone can be effectively used for uranium collection from seawater, wastewater treatment, metal refining, etc.

Furthermore, the method of the present invention is valuable as an efficient method for producing the above-mentioned macrocyclic hexaketone.

Next, the present invention will be explained in more detail with reference to Examples.

Reference example 1 1.8 nonadiyne (CH20(CH2)5CyoCH) 8.82 in 10ml of methylene chloride (CH2Cl2)
(73 mmol) and 1.4 g of 7-octinoyl chloride (CH3C (CH2), COCI) (
8.8 mmol) was added and dissolved, and stannic chloride (Sn
Cl4) 3.45r (13.2 mmol) was added dropwise at 15°C and stirred for 10 minutes.

1.3 ml of water and 5.92 mL of sodium bicarbonate were added to the reaction solution under water cooling, and the mixture was dried over anhydrous sodium sulfate, passed through a column packed with alumina (Woelm, activity M), and eluted with ether.

Ether was evaporated from the eluate, and unreacted 1,8-nonadiyne was recovered from the top of the column by vacuum distillation, and the oily residue was passed through a column packed with alumina (Woelm, activity■) and purified with petroleum ether-ether (2: Elute with 1),
When purified, io-chloroheptadec-9-en-8-one-1,16-diyne (β-chloroenone) (
CH3C' (CU2)5 COCH= CC l
(CH2)s C3cn)o. 4s? (Yield 20
%) and heptadec-8-one-1,9,16-triin(ynone) (CH3C(CH2), COCmiC(C
0.649 g of H2)5CyoCH) was obtained (yield 30%).

Example 1 To 1.0 mmol of β-chloroenone obtained in Reference Example 1 above, pimeryl chloride (CICO (CH2)5COCl )0.2op(
1. The mixture was cooled and dried in the same manner as in Reference Example 1 above, and the solvent was evaporated to obtain an oily mixture.

Further, this oily mixture was refluxed for 5 hours in 30 ml of water-methanol (1:2) containing several drops of sulfuric acid, and then passed through a silica gel packing force ram (petroleum ether-ether (2:2)).
As a result of elution and purification in step 3), colorless needle-shaped crystals of 1,3,9,11,17,19-hexaoquinecyclotetracosane (ketoenolytic tautomer mixture) represented by the above formula (If) were obtained. .129 (yield 29%; yield based on β-chloroenone as a raw material).

) was obtained. The analysis results of the properties of this compound are shown below.

■ Solubility: Slightly soluble in water.

Easily soluble in chloroform, ether, benzene, alcohol, and dimethylformamide.

■ Melting point: 59℃ ■ Absorption peak (cm') of infrared absorption spectrum (KBr tablet method) 1700 (keto type C-0), 1610 (
Enol type c=c, c=o) ■ Proton nuclear magnetic resonance spectrum (solvent 20DCl3, internal standard S t (
CHs) 4) δ: 1.2 -1.4 (br
．． s, 6H), 1.4-1.9(m, 12H),
2. 1-2. 5 (m, 1 2 H), 3.
4 5 (s) + 5.3 7 (s) + 1 4.1 ( b
r. s ) = 6H ■ Mass spectrum peak m/e; 420 (M ), 402, 384, l25C
base) Application example '1 ml of benzene solution of 1,3,9,11,17,l9-hexaoxocyclotetracosane (4.2 mmol) obtained in the above example and uranyl acetate solution (10.pp)
After stirring 5 ml of the solution at room temperature for 20 hours, it was colored with arsenazo and the visible absorption intensity at 665 nm was measured. As a result, the residual uscinyl ion concentration in the aqueous layer was 0.2 ppm (extraction rate 98%). Ta.

The uranyl ions are l, 3, 9, 11, 17, 19-
It formed a very stable complex salt with hexaoxocyclotetracosane.

In addition, dicyclohexyl-1, 4, 7, 10, l3, l
As a result of performing the same operation as above using 6-hexaazacyclooctadecane (dicyclohexyl 18-crown-6), 8.4 ppm of uranyl ions remained in the aqueous layer in a non-complex salt form.

Calculating the metal extraction constant from this result, it is 1, 3, 9,
l1,17,l9-hexaoxocyclotetracosane is 260, than dicyclohexyl-18-crown-6.
It can be seen that the extraction capacity is excellent.

Reference Example 2 In the same manner as in Example 1, 1,8-nonadiyne 1.22 (1
0 mmol) and 1.97 g (10 mmol) of pimeryl chloride were reacted in the presence of 5.2 g (20 mmol) of stannic chloride, and then hydrolyzed in a conventional manner to give 1.3.
Colorless needle-like crystals of 9,11-tetraoxocyclohexadecane 0.955i' (yield 34%, melting point 119-121°C
was gotten.

Claims (1)

[Claims] A macrocyclic hexaketone represented by formula 1. 2 10-chloroheptadec-9-ene-8-one-
A process characterized by reacting 1,16-diyne and/or heptadec-8-one-1,9,16-triyne with pimeryl chloride in the presence of a Lewis acid catalyst, and then hydrolyzing the resulting product. A method for producing a macrocyclic hexaketone represented by the formula. 3. The Lewis acid is one or more compounds selected from the group consisting of tin halide, aluminum halide, boron trifluoride, ferric chloride, zinc chloride, titanium tetrachloride, and cupric chloride. The method according to claim 2.