Calixarene derivatives, their preparation process and their use

Details Calixarene derivatives, their preparation process and their use Calixarene derivatives, their preparation process and their use

1997-10-14

1999-02-02

Bos, Steven

Chemistry of inorganic compounds

Treating mixture to obtain metal containing compound

Radioactive metal

423 10, 423 215, 564 15, 210634, 210638, 210643, C22B 6000, C01F 1700, C07F 902, C07F 928

Patent

active

058660879

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to novel calixarenes derivatives, their preparation process and their use for extracting actinides and lanthanides.
More specifically, it relates to calixarenes having a phosphinoxidoacetamide substituent having interesting properties for extracting actinides and lanthanides, particularly trivalent lanthanides and actinides.
Therefore said novel calixarenes are usable for extracting actinides and lanthanides present in aqueous solutions, such as aqueous effluents from spent nuclear fuel reprocessing installations or spent nuclear fuel dissolving solutions.
Consideration has already been given to the use of macrocyclic ligands such as calixarenes for extracting metals from aqueous solutions. Thus, U.S. Pat. No. 4,477,377 describes the use of calixarenes for recovering cesium from aqueous solutions and WO 94/12502 and WO 94/24138 describe crown calixarenes usable for the selective extraction of cesium and actinides. In the first case, the calixarenes have a special structure, because they have several bridges giving an alternating 1, 3 constellation to the basic structure and giving them both the complexing properties of crown ethers and certain properties of calixarenes (lipophilic character, constellation, etc.).
The present invention relates to novel derivatives of calixarenes which, although having a greater mobility, have good extraction properties with respect to actinides and lanthanides, due to the presence of special substituents.
According to the invention, the calixarene is in accordance with the formula: ##STR2## in which m is equal to 0 or 1, n is an integer from 2 to 8, with 4.ltoreq.n(m+1).ltoreq.8, O-nitrophenoxyalkyl groups and groups.
Thus, the calixarenes according to the invention have no bridge between the benzene units and consequently have a less rigid structure than that of the crown calixarenes of WO 94/12502 and WO 94/24138. In these novel calixarenes, the presence of phosphinoxidoacetamide groups, which are fixed to the upper edge of the cavity of the macrocycle, gives the ligand a very high affinity for actinides and lanthanides.
In the above formula (I), R.sup.1 and R.sup.2 can be alkyl or O-nitrophenoxyalkyl groups. The alkyl groups can be straight or branched and preferably have 1 to 18 carbon atoms.
In said formula, R.sup.3 and R.sup.4 can be alkyl or aryl groups. The alkyl groups can be straight or branched and preferably have 1 to 18 carbon atoms. The aryl groups which can be used are monovalent groups derived from an aromatic or heterocyclic nucleus by removing a hydrogen atom from one of the carbon atoms of the cycle. Examples of such groups are the phenyl, naphthyl, pyridyl, thiophenyl and substituted phenyl groups.
According to a first embodiment of the invention, the calixarenes are in accordance with formula (I) with m equal to 0. Such calixarenes have the same substituents on each edge of the cavity of the macrocycle. They have good extracting properties relative to trivalent actinides and lanthanides.
According to a second embodiment of the invention, the calixarene is in accordance with formula (I) with m equal to 1.
In this case all the substituents on the upper edge of the cavity of the macrocycle are identical and give a lipophilic character to the macrocycle. However, the substituents on the lower edge of the cavity alternate, a methyl group being interposed between two alkyl groups.
Such more soluble calixarenes, particularly in nitrophenyl alkyl ethers, are of interest for the extraction of tetravalent plutonium.
The calixarenes according to the invention can be prepared by a process having the following stages: ##STR3##
in which R.sup.1, R.sup.2, m and n have the meanings given hereinbefore and R.sup.5 is a hydrogen atom or a tert. butyl group, in order to obtain a nitro derivative of formula: ##STR4## b) conversion of the nitro derivative of formula (III) into an amino derivative of formula: ##STR5## by catalytic hydrogenation, c) reacting the amino derivative of formula (IV) with a phosphinoxyidoacetate of formula: ##STR6## in

REFERENCES:
patent: 4548790 (1985-10-01), Horwitz et al.
patent: 5607591 (1997-03-01), Dozol et al.
patent: 5717126 (1998-02-01), Paciello et al.
Chem. Abstracts, vol. 114, No. 15, 15 Apr. 1991, Columbus, OH, US; Abstract No. 143712, Kondo Y et al.: Calixarene Derivatives having Phosphonic Acid Group XP002003481, & JP, A, 90 229 198 (Kanebo, Ltd.; Japan) 11 Sep. 1990.
Chemical Abstract 128:107566, 1996.
Chemical Abstract 125:86742, 1996.

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