Calixarene derivatives

Details Calixarene derivatives Calixarene derivatives

2001-05-29

2003-12-02

Vollano, Jean F. (Department: 1754)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C423S021500

Reexamination Certificate

active

06657081

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to new calixarene derivatives and the preparation method and use of said derivatives to extract actinides and lanthanides.
More specifically, it relates to calixarenes comprising a phosphinoxide-acetamide substituent, offering beneficial properties for the extraction of actinides and lanthanides, particularly trivalent actinides and lanthanides.
Therefore, said new calixarenes may be used to extract actinides and lanthanides present in aqueous solutions such as aqueous effluents from used nuclear fuel reprocessing installations or used nuclear fuel dissolution solutions.
STATE OF THE RELATED ART
The use of macrocyclic ligands such as calixarenes comprising a phosphinoxide-acetamide substituent, to extract metals such as lanthanides and actinides from aqueous solutions has already been envisaged, as disclosed in WO-A-96/23800 [1].
In said derivatives, the phosphinoxide-acetamide substituent is arranged directly on the phenyl cycles of the calixarene.
DESCRIPTION OF THE INVENTION
The present invention relates to new calixarene derivatives comprising a phosphinoxide-acetamide substituent which is separated from the phenyl groups of the calixarene by a hydrocarbon chain. In addition, said phosphinoxide-acetamide substituent is linked to the hydroxyl function of the calixarene by said hydrocarbon chain.
According to the invention, the calixarene complies with the formula:
wherein:
R
1
is an alkyl or aryl group, or a hydrogen atom,
R
2
and R
3
, which may be identical or different, are alkyl or aryl groups,
n is an integer ranging from 2 to 8, and
p is an integer ranging from 4 to 8.
In this calixarene, the presence of a hydrocarbon chain between the phosphinoxide-acetamide group and the phenyl cycle is of interest since it makes it possible to adjust the extraction efficiency of the calixarene with respect to actinides and lanthanides.
Indeed, said efficiency increases with the number of carbon atoms in the hydrocarbon chain (CH
2
)
n
, where the number of carbon atoms n may range from 2 to 8, preferentially from 2 to 5.
In formula I given above, R
1
may represent a hydrogen atom or an alkyl or aryl group. The alkyl groups liable to be used are linear or ramified alkyl groups, preferentially comprising 1 to 18 carbon atoms.
An example of an R
1
group includes the tert-butyl group.
In formula I given above, R
2
and R3 may be alkyl or aryl groups. The alkyl groups may be linear or ramified and preferentially have 1 to 18 carbon atoms. The aryl groups that may be used for R
1
, R
2
and R
3
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 include phenyl, naphthyl, pyridyl, thiophenyl and substituted phenyl groups. Preferentially, R
2
and R
3
represent the phenyl group.
The calixarenes according to the invention may comprise 4 to 8 phenyl cycles. Preferentially, the calixarene comprises 4 phenyl cycles (p=4).
The calixarenes according to formula I according to the invention may be prepared using a method consisting of reacting an amino-alcoxy calixarene derivative according to the formula:
wherein R
1
, n and p are as defined above, with a phosphinoxide-acetate according to the formula:
wherein:
R
2
and R
3
are as defined above and R
4
represents the p-nitrophenyl or 2,4-dinitrophenyl group.
The phosphinoxide acetate according to formula III used in the last step may be prepared using the corresponding alkyl phosphinite according to the formula:
where R
2
and R
3
have the correspondences given above and R
5
is an alkyl group comprising 1 to 4 carbons, by means of a reaction of said group with ethyl bromoacetate, followed by hydrolysis and esterification of the acid obtained with nitrophenol or dinitrophenol.
According to a first embodiment of the invention, the aminoalcoxy calixarene derivative according to formula II wherein n is greater than 2, is prepared using a method comprising the following steps:
1) reaction of a calixarene according to the formula:
 where R
1
and p have the correspondence given above with an N-3(bromoalkyl)phthalimide according to the formula:
 where n has the correspondence given above, to obtain a (3-phthalimido-alcoxy)calixarene according to the formula:
 and
2) reaction of the compound according to formula VI with hydrazine.
According to a second embodiment of the invention, the aminoalcoxy calixarene derivative according to formula II wherein n=2 is prepared using a method comprising the following steps:
1) reaction of a calixarene according to the formula:
 wherein:
R
1
and p have the correspondence given above, with an alkyl bromoacetate, to obtain the calixarene derivative according to the formula:
 where R
1
has the correspondence given above and R
5
represents an alkyl group,
2) reduction of the calixarene derivative according to formula VII to obtain the hydroxylated derivative according to the formula:
3) reaction of the hydroxylated derivative according to formula VIII with tosyl chloride to obtain the tosylated derivative according to the formula:
 wherein Ts represents the tosyl group, and
4) reaction of the tosylated derivative according to formula IX with NaN
3
, followed by a catalytic hydrogenation to obtain the calixarene according to formula II where n=2.
The calixarenes according to formula I of the invention may be used to separate at least one metal selected from actinides and lanthanides present in an aqueous solution, such as dissolution solutions and aqueous effluents from used nuclear fuel reprocessing installations, particularly a nitric solution containing 1 to 4 mol/l of HNO
3
.
To carry out this separation, the aqueous solution containing the metal(s) to be separated is placed in contact with a non-miscible phase comprising at least one calixarene complying with formula I given above, to extract the metal(s) in the non-miscible phase.
Said non-miscible phase is generally composed of a solution of the calixarene(s) according to the invention in a suitable organic solvent.
Examples of solvents that may be used include alkyl benzenes and nitrophenyl alkyl ethers.
Preferentially, an ether such as ortho-nitrophenyl hexyl ether is used as the solvent.
The calixarene concentration of the non-miscible liquid phase particularly depends on the solvent used. Concentrations ranging from 10
−4
to 5.10
−2
mol/l, for example a 10
−3
mol/l concentration, may be used.
To implement the separation method according to the invention, the aqueous solution may be placed in contact with said non-miscible liquid phase in conventional installations such as mixers-clarifiers, centrifugal extractors, pulsating columns, etc., but also by means of supported liquid membranes.
The supported membrane technique consists of immobilising the non-miscible liquid phase on a solid substrate such as polypropylene. Using this technique, it is possible to transfer the metals to be separated from the aqueous solution in which they are contained into an aqueous re-extraction solution. In this case, one of the sides of the membrane is in contact with the first aqueous solution containing the metals to be separated and the other side is in contact with an aqueous re-extraction solution.
The substrate of the supported liquid membrane may be a microporous membrane wherein the pores are filled with calixarene in solution in a suitable organic solvent. Said microporous membrane may be made of polypropylene, polyvinylidene fluoride or polytetrafluorethylene. Said membrane may be used as a separation between a first compartment with the aqueous solution containing the metals to be separated and a second compartment with the aqueous re-extraction solution.
To obtain satisfactory extraction with supported liquid membranes, it is advantageous to use thin, highly porous membranes with a small pore diameter. Said membranes may be used in the form of plane membrane or hollow fibre ultra- or microfiltration mo

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