- 2 -
During the fuel cycle, from the uranium mine to the reprocessing plants, the
radioactive compounds are present in highly varied physicochemical forms
generating different toxicities and thus bringing about highly diversified
risks of exposure to the personnel.
In order to ensure protection of the health of the workers, it is necessary to
carry out medical monitoring. Different examinations are carried out on the
workers, including the analysis of the alpha-emitting actinides eliminated in
the excreta (urine and stools).
Currently, the analytical technique of reference is the a spectrometry. Due
to the short distance covered by a particles in the material, it is impossible
to directly measure uranium, americium and plutonium in urine; it is thus
necessary to manufacture a thin film source for each of the actinides. This
involves a first stage of mineralization of the sample, followed by a
chemical purification which makes it possible to isolate the actinides from
the urinary matrix and to separate them from one another, in order to limit
spectral interferences.
In the protocols currently used by all laboratories for radiotoxicological
analysis, this purification is based on successive separations of the actinides
using appropriate chromatographic columns (Harduin et al.,
Radioprotection, 31, No. 2, 229-245, 1996). These protocols are lengthy (6
days in order to obtain the final result), in the order of 3 days for the
chemical treatment and 3 days of counting by a spectrometry, in order to
achieve levels of activity per isotrope of less than 1 mBq.r-1 of urine.
In the context of continual technological change in the nuclear industry and

- 3 -
of change in regulations, the means which make it possible to routinely
monitor the workers and to evaluate the internal exposure of individuals in
the event of accidents must be improved.
There is thus a real and crucial need in terms of health to be able to have
available, within very short periods of time, results of measurements relating
to uranium, americium and plutonium in order to be able to counter the
deleterious effects of alpha radiation. Making available faster and more
efficient analytical techniques would also make it possible tc monitor a
emitters in the environment, in order to respond to the problems of long-
term development.
Numerous studies have been carried out in order to solve this problem but
none has been successful to date. Research has been directed at specific
complexing agents for the three actinides, in order to extract them from
complex matrices, such as biological media.
The majority of the studies have been carried out on specific complexing
cages: the calixarenes. For example, in 1993, Araki et al. showed the
complexing properties in liquid/liquid extraction of l,3,5-0-trimefhyl-2,4,6-
0-tri(carboxylic acid)-para-tert-butylcalix[6]arene (molecule represented
hereinafter by the formula IA) with regard to uranium (Chem. Lett., 829-
832, 1993). In 1994, Van Duynoven et al. used the same molecule to study
its conformational equilibria (J. Am. Chem. Soc, 116, 5814-5822). In 1997,
C. Dinse et al. (Radioprotection, 32, No. 5, 659-671) demonstrated the
selectivity, in liquid/liquid extraction, of the molecule of formula A with
regard to uranium in the presence of plutonium and sodium.

- 4 -
More recently, a novel extraction agent, a synthetic derivative of the
molecule of formula A, l,3,5-0-trimethyl-2,4,6-0-tri(hydroxamic acid)-
para-tert-butylcalix[6]arene (molecule represented hereinafter by the
formula B), was proposed by Bennoura et al. in Journal of Inclusion
Phenomena and Macrocyclic Chemistry, 40, 95-98, 2001, for the
complexing of cations.

To our knowledge, the molecules of formulae A and B have never formed
the subject of studies on supported membranes or on grafted supports.
The immobilization of calixarenes via a covalent bond on support materials
has already been described by S.P. Alexandratos et al. in Macromolecules,
2001, 34, 206-210, and then in 2002 by Trivedi et al. in Reactive and

- 5 -
Functional Polymers, 50. 205-216. Furthermore, the work by Z. Asfari,
published in 2001 by Kluwer Academic Press (Netherlands) and entitled
"Calixarenes", presents, in the chapter written by R. Milbradt and V.
Böhmer, pages 663 to 676, a review of the immobilization techniques and
the products obtained. However, the immobilization of calixarenes of
formulae A and B has never been described.
None of the products or techniques described in the prior art makes it
possible to analyze uranium and/or americium and/or plutonium cations at a
content in the order of 1 mBq per liter in less than 6 days.
Surprisingly, the inventors have found that the replacement ot a methoxy
group in the formulae A and B described in the literature by another group,
and more advantageously by the hydroxyl group, did not reduce the
complexing capabilities with regard to the uranium, americium and
plutonium cations.
This discovery has been taken advantage of in preparing supported liquid
membranes comprising the compounds of general formulae IA and/or IB
and novel support materials. These membranes and these support materials
exhibit the property of selectively complexing uranium and/or americium
and/or plutonium. The use of these supported membranes in columns
suitable for the analysis by extraction chromatography makes it possible for
the analysis of the abovementioned elements at a content in the order of
1 mBq/1.
Thus, the present invention relates to a novel family of para-tert-
butylcalix[6]arene compounds of formula (IA) or (IB)

- 6 -

where R1, R3 and R5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30, carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation,
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,

- 7 -
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses;
with the following conditions:
Rl, R3 and R5 not simultaneously representing CH3 in (IA) and (IB),
Rl, R3 and R5 not simultaneously representing CH2COOH in (IA), and
Rl, R3 and R5 not simultaneously representing CH2CONHOH in (IB).
According to an advantageous embodiment, in formula (IA) and (IB), two
from Rl, R3 and R5 represent hydrogen or methyl, the third being chosen
from (vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses.
According to another advantageous embodiment, the para-tert-
butylcalix[6]arenes of the invention are compounds of formula (IA) or (IB)
in which Rl, R3 and R5 are identical and preferably represent a hydrogen.

- 8 -
The invention also relates to supported liquid membranes comprising a para-
tert-butylcalix[6]arene of formula (IA) or (IB)

where R1, R3 and R5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30, carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation.

- 9 -
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses;
said product of formula (IA) or (IB) being dissolved in an organic solvent
and absorbed on a support.
The organic solvent according to the invention exhibits a boiling point of
greater than 60°C, so as to limit the evaporation of said solvent during
storage. Furthermore, it must have good solubility properties with regard to
the calixarenes of the invention. The following will be noted among the
most advantageous solvents, without, however, this list being limiting:
toluene, xylene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, 1,4-
diisopropylbenzene, hexylbenzene, kerosene, tetrahydropyran, 1,2,3,4-
tetrahydronaphthalene, pentanol and higher homologous alcohols, glycols
and their ethers, such as, for example, diethylene glycol dibutyl ether, esters,

- 10 -
such as methyl benzoate, or ethers, such as ortho-nitrophenyl pentyl ether or
nitrophenyl octyl ether.
By way of example, the solubilities in mol/1 of the compound IA in various
solvents are as follows: at 25°C
1,2-dichlorobenzene: 3.13 x 10-3 M, chlorobutane: 1.6 x 10-3 M, isooctane:
1.25 x 10"3 M, isobutyl acetate: 1.75 x 10"3 M, tert-butyl acetate: 5.25 x 10-
3 M, isoamyl benzoate: 2.40 x 10"3 M, benzylacetate: 3.71 x 10"3 M, methyl
benzoate: 6.41 x 10"3 M, benzonitrile: 1.81 x 10'3 M, 1-hexanol: 17.65 x 10-
3 M, 1-heptanol: 14.28 x 10"3 M, diethylene glycol dimethyl ether:
23.53 x 10-3M, diethylene glycol tert-butyl ethyl ether: 11.34 x 10-3 M,
diethylene glycol dibutyl ether: 19.33 x 10"3 M, dipentyl ether: 2.32 x 10"
3 M, isoamyl ether: 2.02 x 10"3 M, isobutyl ether: 1.58 x 10-3M, 1,1,2-
trichlorotrifluoroethane: 1.57 x 10-3 M, 1,2,3,4-tetrahydronaphthalene:
6.4 x 10-3M.
The constituent support materials of the supported liquid membranes of the
invention are of inorganic origin, chosen from the group comprising of silica
gels, oxides, such as alumina, zirconia and titanium oxide, or of organic
origin, chosen from the group comprising of polystyrene/divinylbenzenes,
polyethers, polyacrylamides and poly(glycidyl methacrylate)s, or of organo-
inorganic origin, chosen from the group comprising of silica/dextran and
hydroxyapatite/agarose composites, and their mixtures.
Preferably, the support is in the form of particulates, the particle size varying
between 10 nm and 10 mm, preferably between 10 and 50 microns, and the
porediameter varying between 10 and 5000 A, preferably between 100 and
500 A.

- 11 -
The invention also relates to the liquid membranes present in the supported
liquid membranes, that is to say to the para-tert-butylcalix[6]arenes of
formulae (IA) and (IB), in solution in a solvent, the solvent being a water-
insoluble organic solvent as described above.
The invention also relates to a support material which is a para-tert-
butylcalix[6]arene of formula (IIA) or (IIB)

where R'1, R'3 and R'5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,

- 12 -
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30, carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation,
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl mefhacrylate)s, dextrans and
agaroses;
(vii) -SPACER-SUPPORT,
the SPACER being a divalent radical chosen from the group comprising of
C1-C60, preferably C1-C30, alkylenes, (C1-C60 alkyl)arylenes, aryl(C1-C60
alkylenes) and aryl(C1-C60 alkyl)aryls, it being possible for the divalent
radical to be substituted by halogen atoms, organometallic compounds,
alcohol, amine, acid, ester, carbamate, thiocarbamate, ether, thiol, epoxide,
thioepoxide, isocyanate or isothiocyanate functional groups or it being
possible for a carbon of this divalent radical to be replaced by a nitrogen,
sulfur, phosphorus, oxygen, boron or arsenic heteroatom;

- 13 -
the SUPPORT being chosen from supports of inorganic or organic or
organo-inorganic origin, preferably particulate supports, the particle size of
which varies between 10 nm and 10 mm, preferably between 10 and 50
microns, and the pore diameter of which varies between 10 and 5000 A,
preferably between 100 and 500 A;
provided that at least one of R' 1, R'3 or R'5 is a (vi) or (vii) group.
A support material is constituent of the stationary pnase of a
chromatographic column.
In the support material of the invention, the SUPPORT is of inorganic
origin, chosen from the group comprising of a silica gel, oxides, such as
alumina, zirconia and titanium oxide, or of organic origin, chosen from the
group comprising of polystyrene/divinylbenzenes, polyethers,
polyacrylamides and poly(glycidyl methacrylate)s, or of organo-inorganic
origin, chosen from the group comprising of silica/dextran or
hydroxyapatite/agarose composites.
This SUPPORT results from a support comprising reactive chemical
functional groups, it being possible for said chemical functional groups to be
organic or inorganic, such as, for example, carboxylic acid chloride, amine,
aldehyde, thiol, sulfonyl chloride, isocyanate or metal halide functional
groups, without, however, this list being limiting.
By way of example, functionalized particulate supports are the copolymer of
[5-(4-(chloromethyl)phenyl)pentyl]styrene and of divinylbenzene and also
the copolymer of [5-(4-(bromomethyl)phenyl)pentyl]styrene and of
divinylbenzene, and the copolymer of 4-(chloromethyl)styrene and of
divinylbenzene.

- 14 -
They can be provided in the form of spherical or irregular solid particles, the
particle size of which can vary, and also the porosity. Various commercial
grades are available, such as the Stratosphere* resins sold by Aldrich.
The following procedure is used to synthesize the novel compounds of
general formula IA and IB:
a compound l,3,5-trimethoxy-para-terM)utylcalix[6]arene of formula (a)

is synthesized and then a precursor compound 2,4,6-tri(ethyl ester)-1,3,5-
trimethoxy-para-tert-butylcalix[6]arene of formula (b)


- 15 -
is synthesized.
The compound of formula (b) is then optionally subsequently modified, by
saponification or by substitution of the carboxylic acid ethyl ester functional
groups, to result in the compounds of formula A or B.
The compound of formula (b) can also be partially or completely
demethylated, to result in the compounds of general formula (c1), (c2) or
(c3).



- 16 -
The compounds of formula (c1) or (c2) or (c3) are subsequently modified by
chemical modification of the hydroxyls to result, on the one hand, in
compounds of the general formula (IA), by saponification of the ethyl esters,
or, on the other hand, in compounds of general formula (IB), by producing
hydroxamic acid functional groups from the ethyl esters.
According to an alternative form of the process, the compounds of formula
(c1) or (c2) or (c3) can subsequently be directly reacted with suitably
functionalized supports to result in covalent grafting reactions via the
activation of their free phenolic hydroxyls, in order to result, on the one
hand, in support materials of general formula (IIA), by saponification of the
ethyl esters, or, on the other hand, in support materials of general formula
(IIB), by producing hydroxamic acid functional groups from the ethyl esters.
Thus, a support material in accordance with the invention can also be
represented in the following way:


- 17 -
The details of the stages of this synthesis are given below:
A) synthesis of l,3,5-trimethoxy-para-tert-butylcalix[61arene (RM =1014)
The process consists in synthesizing, in a first step, a common precursor
comprising carboxylic acid ester functional groups in the 2, 4 and 6
positions and trimethoxy functional groups in the 1, 3 and 5 positions.
During this objective, it is first necessary to synthesize a symmetrical
compound l,3,5-trimethoxy-p-tert-butylcalix[6]arene (RM = 1014) of
formula (a) above.
Commercial para-tert-butylcalix[6]arene is dissolved in anhydrous acetone.
Potassium carbonate is added and the suspension is stirred under nitrogen
for 3 hours. Excess methyl iodide is then added and the reaction suspension
is gradually brought to reflux for 24 hours with stirring.
The acetone is subsequently evaporated to dryness under the vacuum of a
laminar flow pump on a water bath adjusted to 60°C. The solid residue
obtained from the drying operation is dissolved in chloroform. After

- 18 -
dissolution, water is added and the two-phase medium is placed under
vigorous stirring and then acidified using 12M concentrated hydrochloric
acid. The lower organic phase is subsequently recovered by separation by
settling and then washed with water until the aqueous washing liquor
present in the upper phase is neutral. The lower organic phase is
subsequently dried over anhydrous sodium sulfate and then filtered. The
clear organic phase is concentrated to dryness on a water bath at 60°C under
laminar flow vacuum. The drying residue is subsequently purified by low-
pressure chromatography on silica gel of chromatographic grade. The eluent
used is pure synthetic methylene chloride stabilized with amylene. The
purity of the various fractions is monitored in methylene chloride/ethanol
95/5 by TTC on virgin silica plates.
The fractions comprising the symmetrical compound 1,3,5-trimefhoxy-p-
ferf-butylcalix[6]arene, single spot by TTC (visualization by iodine vapor),
are combined and then concentrated to dryness.
The residue is used as is in the following stage.
B) synthesis of 2,4,6-tri(ethyl ester)-1,3,5-trimethoxy-para-tert-
butvlcalix[61arene (RM = 1272.5) (formula (b))
In a second step, the process consists in synthesizing the common precursor,
comprising carboxylic acid ester functional groups in the 2, 4 and 6
positions and trimethoxy functional groups in the 1, 3 and 5 positions, by
modifying all the phenolic hydroxyls of the compound obtained above
which are located in the 2, 4 and 6 positions, the 1,3 and 5 positions being
protected by the methoxy groups.
The product obtained in the preceding example (formula (a)) is dissolved in
anhydrous DMF (dimethylformamide) (dried over sodium hydride) under a
nitrogen atmosphere. A very large excess of cesium carbonate is added and

- 19 -
the suspension obtained is stirred under nitrogen for 4 hours. A very large
excess of ethyl bromoacetate is subsequently run in over 5 minutes onto the
reaction suspension and the vigorously stirred medium is gradually brought
to reflux for 24 hours while bubbling nitrogen through.
The DMF is evaporated to dryness under the vacuum of a laminar flow
pump on a water bath adjusted to 80°C. The solid residue obtained from the
drying is dissolved in chloroform. After dissolving, water is added and the
two-phase medium is placed under vigorous stirring and then acidified with
12M concentrated hydrochloric acid. The lower organic phase is
subsequently washed several times with water and then it is dried over
anhydrous sodium sulfate. After filtering, the organic phase is concentrated
to dryness on a water bath at 60°C under laminar flow vacuum. The drying
residue is taken up in ethanol. A white suspension is obtained. The white
solid is recovered by filtration. It is washed several times on the filter with
ethanol and then dried in an oven at 40°C under vacuum.
C) synthesis of 2,4,6-tri(ethyl ester)-l-hydroxy-3,5-dimethoxy-para-tert-
butylcalix[6]arene (compound (c1))
2,4,6-tri(ethyl ester)-1,3-dihydroxy-5-monomethoxy-para-tert-
butylcalix[6]arene (compound (c2))
2,4,6-tri(ethyl ester)-1,3,5-trihydroxy-para-ferf-butylcalix[6]arene
(compound (c3))
In an optional third stage, the process consists in partially or completely
demethylating the common precursor of formula (b), comprising carboxylic
acid ester functional groups in the 2, 4 and 6 positions and both phenolic
hydroxyl and methoxy functional groups in the 1, 3 and 5 positions
(compounds (cl) or (c2)) or solely phenolic hydroxyl groups in the 1,3 and
5 positions (compound (c3)).

- 20 -
To do this, the compound of formula (b) obtained above is dissolved in
anhydrous chloroform dried beforehand over sodium hydride. The medium
is stirred under a nitrogen atmosphere and then trimethylsilyl iodide
(demethoxylating agent for calixarenes) is added, in stoichiometric amount
or in deficit depending on whether it is desired to favor mono-, di- or
tridemethylation, and the reaction medium is brought to reflux for 2 hours
while bubbling nitrogen through. The reaction kinetics are determined by
TLC monitoring in toluene/ethyl acetate 90/10 on a silica/polyester plate.
Trimethylsilyl iodide is optionally again added all at once after cooling the
reaction medium, depending on the kinetics of formation of the desired
entities (molecules of formula (c1) or (c2) or (c3)). The reaction medium is
again gradually brought to reflux for 2 hours or more.
The reaction is halted by the addition of water. The reaction medium is
acidified with 1M HC1 and the lower organic phase, which is brick red, is
recovered by separation by settling. It is washed with water until the
aqueous washing liquor (upper phase) is of neutral pH.
After drying over anhydrous sodium sulfate, the lower chloroform phase is
evaporated to dryness under the vacuum of a laminar flow pump on a water
bath adjusted to 60°C. Residue obtained from the drying is subsequently
purified by low-pressure chromatography on silica gel of chromatographic
grade. The eluent used is the toluene/ethyl acetate 90/10 mixture. The purity
of the various fractions is monitored in the toluene/ethyl acetate 90/10
mixture by TLC on plates of virgin silica deposited on a polyester support.
The fractions comprising the compounds (cl) or (c2) or (c3) are combined
and brought to dryness separately under the evaporation conditions
described above.
Each residue from the drying operation is used as is for possible subsequent
chemical modifications.

- 21 -
D) synthesis of 2,4,6-tri(ethyl ester)- 1-R 1-3.5 -dimethoxy-para-tert-
butylcalix[6]arene (compound (d1))
2,4,6-tri(ethyl ester)-1,3-R1,R3-5-monomethoxy-para-tert-
butylcalix[6]arene (compound (d2))
2,4,6-tri(ethyl ester)-l,3.5-Rl,R3,R5-para-tert-butylcalix[6]arene
(compound (d3Y)
In another optional stage, the process consists in synthesizing a compound
of general formula (dl) or (d2) or (d3) from respectively the compounds
(c1) or (c2) or (c3) obtained above. The phenolic hydroxy 1 functional groups
in the 1 and/or 3 and/or 5 positions are modified and R1 and/or R3 and/or
R5 groups are introduced, it being known that they cannot represent
hydroxyls or methyls.
To do this, a compound of formula (c1) or (c2) or (c3) obtained above is
dissolved in anhydrous DMF (dimethylformamide) (dried over sodium
hydride) under a nitrogen atmosphere. A very large excess of cesium
carbonate is added and the suspension obtained is stirred under nitrogen for
4 hours. A very large excess of halide, the organic residue of which
represents the R1 or R3 or R5 group, is subsequently run in in 5 minutes
onto the reaction suspension and the vigorously stirred medium is gradually
brought to reflux for 24 hours while bubbling nitrogen through.
The DMF is evaporated to dryness under the vacuum of a laminar flow
pump on a water bath adjusted to 80°C. The solid residue obtained from the
drying is dissolved in chloroform. After dissolving, water is added and the
two-phase medium is placed under vigorous stirring and then acidified with
12M concentrated hydrochloric acid. The low organic phase is subsequently
washed several times with water and then it is dried over anhydrous sodium
sulfate. After filtering, the organic phase is concentrated to dryness on a
water bath at 60°C under laminar flow vacuum. The drying residue is taken
up in chloroform.

- 22 -
After drying over anhydrous sodium sulfate, the lower chlorofcrm phase is
evaporated to dryness under the vacuum of a laminar flow pump on a water
bath adjusted to 60°C. The drying residue obtained is subsequently purified
by low-pressure chromatography on silica gel of chromatographic grade.
The eluent used is the toluene/ethyl acetate 90/10 mixture. The purity of the
various fractions is monitored in the toluene/ethyl acetate 90/10 mixture by
TLC on plates of virgin silica deposited on a polyester support.
The fractions comprising the compound (d1) or (d2) or (d3) are combined
and brought to dryness separately under the evaporation conditions
described above.
The drying residue is used as is for possible subsequent chemical
modifications.


- 23 -

formula (d3)
E) grafting to a support of one of the following compounds: (c1), (c2), (c3),
(d1), (d2), (d3)
In another optional stage, the process consists in covalently grafting, to a
support, a compound of formula (c1) or (c2) or (c3) or (d1) or (d2) or (d3)
comprising carboxylic acid ester functional groups in the 2, 4 and 6
positions and both phenolic hydroxyl and methoxy functional groups in the
1 and/or 3 positions (compounds (cl) or (c3)) or solely phenolic hydroxyl
groups in the 1,3 and 5 positions (compound (c3)), or R1 and/or R3 and/or

- 24 -
R5 functional groups (where Rl, R3 and R5 are other than hydrogen and
methyl) in the 1, 3 or 5 positions (compounds (dl), (d2) and (d3)).
A compound of formula (c1) or (c2) or (c3) or (d1) or (d2) or (d3) is
dissolved in anhydrous dimethylformamide dried beforehand over sodium
hydride. The medium is stirred under nitrogen until dissolution is complete.
A very large excess of cesium carbonate is added, followed by a commercial
resin of known and quantified functionality, said functionality being chosen
in order to be able to react with a phenolic hydroxyl or with an Rl and/or R3
and/or R5 group, and the reaction medium is brought to 60°C for 72 hours
while bubbling nitrogen through.
The reaction suspension is filtered and the solid is washed with DMF, then
with acetone and then with 1M HC1 until the aqueous washing liquor is of
acidic pH. The resin is subsequently washed with water to neutrality and
then with ethanol.
F) synthesis of a compound of general formula HA
In one option of the process, use is made of a compound of general formula
(a) or (c1) or (c2) or (c3) or (d1) or (d2) or (d3) or a compound obtained by
using the process described in part E.
Said compound is dissolved or suspended in ethanol. An aqueous potassium
hydroxide solution, in very large excess with respect to the stoichiometry
calculated with regard to the number of ethyl ester groups to be saponified,
is added and the medium (solution or suspension) is brought to reflux for 4
hours.
The reaction mass is cooled and the medium is acidified with 12M HC1.

- 25 -
The suspension is filtered and the precipitate (or the support) is washed with
water until the aqueous filtration liquors are of neutral pH and then with
ethanol.
The solid is dried at 40°C under vacuum to constant weight.
G) synthesis of a compound of formula IIB
In one option of the process, use is made of a compound of general formula
(a) or (c1) or (c2) or (c3) or (d1) or (d2) or (d3) or a compound obtained by
using the process described in part E.
Said compound is dissolved or suspended in THF. A methanolic
hydroxylamine hydrochloride solution, in excess with respect to the
stoichiometry calculated with regard to the number of the ethyl ester groups.
is added. A second solution, comprising potassium hydroxide flakes
dissolved beforehand in a methanol/THF mixture and maintained at +5°C, is
then added. The medium (solution or suspension) is stirred at ambient
temperature for 7 days under a nitrogen atmosphere.
The reaction mass is evaporated to dryness on a water bath at 60°C under
vacuum.
The residue is taken up in methylene chloride and then acetic acid is added.
The medium is stirred at 20-25°C for 4 hours and then it is again dried.
The reaction mass is evaporated to dryness on a water bath at 60°C under
vacuum.
The invention also relates to the use of a supported liquid membrane as
described above and/or of a support material according to the invention for
the selective complexing and the analysis of the elements uranium,
americium and plutonium or other radioelements in their cationic form.

- 26 -
The invention also relates to the use of a supported liquid membrane and/or
of a support material according to the invention for removing, from a
mixture of at least two constituents chosen from the group comprising of
organic, inorganic and organo-inorganic molecules, at least a portion of one
of these constituents or for separating said constituents by a
chromatographic method.
The supported liquid membranes and the support materials of the invention
are particularly suitable for exclusion chromatography. They make possible
the detection and separation of minute amounts of product, in particular the
separation of uranium and/or plutonium and/or americium at contents of the
order of 1 mBq/1.
The invention will be described in more detail below with the help of the
following examples, which are given by way of illustration and are not
limiting.
EXAMPLES:
EXAMPLE 1:
Support material comprising 3,5-dimethoxy-2,4,6-tri(carboxylic acid)-
p-tert-butylcalix[6]arene
1-1: synthesis of l,3,5-trimethoxy-p-tert-butylcalix[6]arene (RM = 1014)

- 2 7 -

194.7 g of p-tert-butylcaljx[6]arene (0.2 mol, RM = 972) and 15 1 of
anhydrous acetone are introduced into a 20-liter glass reactor equipped with
a condenser. The medium is stirred under nitrogen until dissolution is
complete. 82.9 g of potassium carbonate (0.6 mol) are added and the
suspension is stirred for 3 hours under nitrogen. 113.6 g of methyl iodide
(0.8 mol) are run in in 5 minutes and the stirred reaction medium is
gradually brought to reflux for 24 hours.
The acetone is evaporated to dryness under the vacuum of a laminar flow
pump on a water bath adjusted to 60°C. The solid residue obtained from the
drying is dissolved in 5.0 1 of chloroform. After dissolving, 1.0 1 of water is
added and the two-phase medium is placed under vigorous stirring. 0.1 1 of
12M concentrated hydrochloric acid is gently added according to the release
of carbon dioxide gas. The organic phase is subsequently washed 5 times
with 1.0 1 of water and then dried over 200 g of anhydrous sodium sulfate.
After filtering, the organic phase is concentrated to dryness on a water baih
at 60°C under laminar How vacuum. 250 g of drying residue are obtained
and are subsequently purified by low-pressure chromatography on 15 kg of
40-200 μm silica gel (60 A pore). The eluent used is methylene chloride
(40 1).

- 28 -
The purity of the various fractions is monitored in methylene
chloride/ethanol 95/5 by TLC on virgin silica plates.
40 g of residue, resulting from the fractions comprising pure 1,3,5-
trimethoxycalixarene, are obtained (39.45 mmol: yield = 19.7%).
The proton NMR spectrum in CDCl3 gives the following chemical shifts:
7.00 ppm (s, 6H, ArH meta OH), 6.90 ppm (s, 6H, ArH meta OCH3),
6.75 ppm (s, 3H, OH), 3.89 ppm (s, 9H, OCH3), 3.47 ppm (s, 12H,
ArCH2Ar), 1.20 ppm (s, 27H, tert-butyl para OH), 1.00 ppm (s, 27H, tert-
butyl para OCH3).
1-2: synthesis of 2,4,6-tri(ethyl ester)-l,3,5-trimethoxy-p-fcrf-
butylcalix[6]arene (RM = 1272.5)

40.0 g of product obtained in 1-1 (39.45 mmol) and 4 1 of anhydrous
dimethylformamide (DMF) (dried over sodium hydride) are introduced into
a 10-liter glass reactor equipped with a condenser. The medium is stirred
under nitrogen until dissolution is complete. 81.6 g of cesium carbonate
(0.25 mol) are added and the suspension is stirred for 4 hours under

- 29 -
nitrogen. 52.7 g of ethyl bromoacetate (0.31 mol) are run in in 5 minutes and
the stirred reaction medium is gradually brought to reflux for 24 hours while
bubbling nitrogen through.
The DMF is evaporated to dryness under the vacuum of a laminar flow
pump on a water bath adjusted to 80°C. The solid residue obtained from the
drying is dissolved in 2.0 1 of chloroform. After dissolving, 0.5 1 of water are
added and the two-phase medium is placed under vigorous stirring. 20 ml of
12M concentrated hydrochloric acid are gently added as a function of the
release of carbon dioxide gas. The organic phase is subsequently washed 5
times with 0.5 1 of water and then dried over 20 g of anhydrous sodium
sulfate. After filtering, the organic phase is concentrated to dryness on a
water bath at 60°C under laminar flow vacuum. The residue is taken up in
300 ml of ethanol. A white suspension is obtained. The solid is recovered by
filtration, washed with 3 times 40 ml of ethanol and then dried in an oven at
40°C under vacuum.
43.2 g of white powder are obtained after drying to constant weight
(33.95 mmol: yield = 86%).
The proton NMR spectrum in CDC13 gives the following chemical shifts:
6.71 ppm (broad s, 12H, ArH meta), 4.55 ppm (s, 6H, ArCH2C02R),
4.29 ppm (qt, 6H, 0-CH2-methyl J = 7 Hz), 3.47 ppm (s, 21H, ArCH2Ar +
methyl OCH3), 1.38 ppm (s, 54H, tert-butyl), 1.33 ppm (t, 9H, methyl
OCH2CH3 J = 7 Hz).
1-3: synthesis of l-hydroxy-3,5-dimethoxy-2,4,6-tri(ethyl ester)-p-tert-
butylcalix[6]arene (RM - 1258.5)

- 30 -

27.8 g of product (white powder) obtained in 1-2 above (21.85 mmol, RM ~
1272.5) and 1.5 l of anhydrous chloroform dried beforehand over sodium
hydride are introduced into a 5-liter glass reactor equipped with a condenser.
The medium is stirred under nitrogen until dissolution is complete. 3.1 ml
(4.37 g) of trimcthylsilyl iodide (21.85 mmol. RM - 200.1) are added and
the reaction medium is brought to reflux for 2 hours while bubbling nitrogen
through. The reaction kinetics are determined by TLC monitoring in
toluene/ethyl acetate 90/10 on a silica/polyester plate. 3.1 mi (4.37 g),of
triniethylsilyl iodide are again added ail at once after cooling the reaction
medium. The latter is again gradually brought to reflux for 2 hours.
The reaction is halted by addition of 2 1 of water. 100 ml of 1M HC1 are
added and the brick red organic phase is recovered. It is washed with 2. times
11of water
After drying with 2.00 g of anhydrous sodium sulfate, the chioroform phase
is evaporated to dryness ander the vacuum of a laminar flow pump on a
water bath adjusted to 60°C. 27.2 g of drying residue are obtained and are
subsequently purified by low-pressure chromatography on 3 kg of 40-
200 um silica gel (60 A pore). The eluent used is a toluene/ethyl acetate
90/10 mixture (20 1). The purity of the various fractions is monitored in the

- 31 -
toluene/ethyl acetate 90/10 mixture by TLC on plates of virgin silica
deposited on a polyester support.
8.5 g of residue are obtained (6.75 mmol: yield = 30.7%) after drying, on a
water bath at 60°C under vacuum, the, fractions comprising che pure 1-
hydroxy-3,5-dimethoxy-2,4,6-tri(ethylester)-p-tert-butylcalix[6]arene.
The mass spectrum, recorded in FAB with positive chemical ionization,
confirms the presence of the expected product (MH+ at 1259 daltons).
The proton NMR spectrum in CDC13 gives the following chemical shifts:
6.75 ppm (s, 13H, ArH meta + OH phenol), 4.55 ppm (s, 6H, ArCH2C02R),
4.29 ppm (qt, 6H, 0-CH2-methyl J = 7 Hz), 3.47 ppm (s, 20H, ArCH2Ar +
methyl OCH3), 1.38 ppm (s, 54H, tert-butyl), 1.33 ppm (t, 9H, methyl
OCH2CH3).
1-4: Support material comprising 3,5-dimethoxy-2,4,6-tri(ethyl ester)-p-tert-
butylcalix[6]arene


- 32 -
8.5 g of product obtained in 1-3 above (6.75 mmol, RM = 1258.5) and
150 ml of anhydrous DMF dried beforehand over sodium hydride are
introduced into a 250 ml glass reactor equipped with a condenser. The
medium is stirred under nitrogen until dissolution is complete. 20 g of
cesium carbonate (61 mmol) are added, followed by 10 g of commercial
polystyrene resin modified with chloromethylphenylpentyl (purchased from
Aldrich CMPP resin: [5-[4-(chloromethyl)phenyl]pentyl]styrene, polymer
bound reference 513776), and the reaction medium is brought to 60°C for 72
hours while bubbling nitrogen through.
The reaction suspension is filtered and the solid is washed with DMF (2
times 50 ml), then with acetone (3 times 50 ml), then with 1M HO (4 times
100 ml), then with water (5 times 100 ml) and then with ethanol (3 times
50 ml).
16.15 g of dry resin are obtained after drying at 60°C under vacuum to
constant weight.
Its degree of grafting, calculated from the microanalysis, is 0.2 mmol of
calix/g of resin.
The microanalysis is as follows:
C%: 80.80 H%:7.29 Cl %: 0.79
The microanalysis of the starting chloromethylphenylpentyl resin was as
follows:
C%: 86.52 H%:7.87 Cl %: 3.91
1-5: Support material comprising 3,5-dimethoxy-2,4,6-tri(carboxylic acid)-
p-tert-butylcalix[6]arene

- 33 -

10 g of dry resin obtained in 1-4 above and 100 ml of ethanol are introduced
into a 250 ml glass reactor equipped with a condenser. 6.1 g of 85%
potassium hydroxide pellets are dissolved in 100 ml of water and the
solution obtained is added all at once to the reactor. The reaction medium is
brought to reflux for 4 hours while bubbling nitrogen through.
The reaction suspension is cooled and then 12 ml of 12M HC1 are added.
The pH of the suspension is 1. After stirring for 1 hour, the suspension is
filtered and then the filter residue is washed with 8 times 100 ml of water
and then with ethanol (3 times 50 ml).
9.7 g of resin are obtained after drying at 60°C under vacuum to constant
weight.
The resin is used as is without additional analytical characterization.
EXAMPLE 2:
Supported liquid membrane comprising l,3,5-trimethoxy-2,4,6-
tri(hydroxamic acid)-p-tert-butylcalix[6]arene (RM = 1234.6)

- 34 -

1.8 g of product obtained in example 1-2 (1.4 mmol) and 50 ml of
tetrahydrofuran (THF) are introduced into a 250 ml glass reactor equipped
with a condenser. 2.02 g of hydroxylamine hydrochloride (29 mmol) are
dissolved in 80 ml of methanol and 40 ml of THF and then the solution
obtained is added to that present in the reactor. Subsequently, another
solution prepared beforehand (and maintained at +5°C) of potassium
hydroxide flakes (2.04 g at 100%, i.e. 36 mmol) in 24 ml of methanol and
12 ml of THF is added all at once to the reactor. The reaction medium is
stirred at ambient temperature for 7 days while bubbling nitrogen through.
The reaction suspension is evaporated to dryness on a water bath at 60°C
under vacuum. The residue is taken up in the methylene chloride/acetic acid
50 ml/10 ml mixture and stirred for 4 hours. The reaction mass is brought to
dryness on a water bath at 60°C under vacuum.
The drying residue is taken up in 20 ml of dichloromethane. The expected
product precipitates in the form of a white solid.
1.5 g of white solid are obtained after drying at 60°C under vacuum to
constant weight (yield = 85.9%).
The mass spectrum, recorded in electrospray ESI, confirms the presence of
the expected product (mz at 1234 daltons).

- 35 -
The proton NMR spectrum at 300 MHz in DMSO gives the following
chemical shifts:
10.8 ppm (s, 3H, -NH), 9.08 ppm (s, 3H, -OH of hydroxamic), 7.23 ppm (s,
6H, ArH meta OCH2COOEt), 6.57 ppm (s, 6H, ArH meta OCH3), 4.44 to
4.33 ppm (q, 18H, ArCH2C02R + ArCH2Ar), 2.50 ppm (broad s, 9H,
methoxy), 1.36 ppm (s, 27H, tert-butyl para OCH2CONHOH). 0.73 ppm (s,
27H, tert-butyl para OCH3).
2 g of resin, Macroprep epoxy, from BioRad, particle size of 70 to 100 fim,
batch 11/99, are added to the solution prepared beforehand of 15.6 mg of
white solid obtained above, withdrawn from the 1.5 g of white solid
obtained beforehand, dissolved in 20 ml of dichloromethane and 1.12 ml of
1,2,3,4-tetrahydronaphthalene. The suspension is gently evaporated at
ambient temperature to constant weight: a white solid is obtained.
Weight obtained: 2.2 g
EXAMPLE 3:
Supported liquid membrane comprising l,3>5-trimethoxy-2,4,6-
tri(carboxylic acid)-p-tert-butylcalix[6]arene (RM = 1174.4)

5.9 g of product (white powder) obtained in example 1-2 (4.00 mmol) and
150 ml of ethanol are introduced into a 250 ml glass reactor equipped with a

- 36 -
condenser. A solution prepared beforehand (and maintained at +5°C) of
potassium hydroxide flakes (12 g at 100%, i.e. 214 mmol) in 150 ml of
water is added all at once to the reactor. The reaction medium is brought to
reflux for 4 hours while bubbling nitrogen through.
25 ml of 12M HC1 are slowly added after cooling the reaction mass to 20°C.
The expected product precipitates in the form of a white solid. A suspension
is subsequently filtered and the solid is washed with 8 times 50 ml of water
and then 2 times 50 ml of ethanol. The solid is subsequently dried at 40°C
under vacuum to constant weight.
4.2 g of white solid are obtained after drying at 40°C under vacuum to
constant weight (yield = 99%).
The proton NMR spectrum at 300 MHz in CDC13 gives the following
chemical shifts:
6.97 ppm (s, 6H, ArH meta OCH2COOH), 6.94 ppm (s, 6H, ArH meta
OCH3), 3.84 ppm (s, 6H, ArCH2COOH), 3.73 ppm (broad s, 9H, methoxy),
1.12 ppm (s, 27H, tert-butyl para OCH2COOH), 1.09 ppm (s, 27H, tert-butyl
para OCH3).
2 g of resin, Macroprep epoxy, from BioRad, particle size of 70 to 100 \im,
batch 11/99, are added to the solution prepared beforehand of 12.5 mg,
withdrawn from 4.2 g of white solid obtained above, dissolved in 20 ml of
dichloromethane and 1.12 ml of 1,2,3,4-tetrahydronaphthalene. The
suspension is gently evaporated at ambient temperature to constant weight.
A white solid is obtained.
Weight obtained: 2.2 g
EXAMPLE 4:
Selective complexing and extracting of americium

- 37 -
In this example, the americium present at a concentration of 10-11 mol.1-1 in a
0.04 mol.l-1 aqueous NaN03 solution simulating the urinary medium and
adjusted to pH = 4 is fixed using the calixarenes of the invention.
For this experiment, use is made of 100 mg of support material from
example 1-5 packaged in a column.
A 0.04 mol.l-1 NaN03 solution at pH = 4 is passed through the column in
order for optimum extraction conditions to exist (conditioning stage). The
aqueous solution comprising the americium is subsequently passed through
the column (fixing stage). A 0.04 mol.l-1 NaN03 solution at pH = 4 is again
passed in order to remove the americium not extracted by the calixarene
(rinsing stage). The fixed americium is finally eluted with a 2M HNO3
solution (elution stage). The solutions flow by natural gravitation. The
americium is measured by alpha spectrometry in each solution at the column
bottom. The results of the measurements make it possible to calculate the
fixing yield and the elution yield for the americium.
The results of this experiment are given in table I below.
EXAMPLE 5:
Selective complexing and extracting of uranium
In this example, the uranium present at a concentration of 10-8 mol.1-1 in a
0.04 mol.l-1 aqueous NaN03 solution simulating the urinary medium and
adjusted to pH = 4 is fixed by means of the calixarenes of the invention.
For this experiment, use is made of 1 g of supported liquid membrane from
example 2 packaged in a column.
The conditioning, fixing and rinsing stages are identical to those described
in example 4. The fixed uranium is eluted with a 1M HNO3 solution. The
uranium is measured by alpha spectrometry or by mass spectrometry (ICP-
MS) in each solution at the column bottom. The results of the measurements

- 38 -
make it possible to calculate the fixing yield and the elution yield for the
uranium.
The results obtained are given in table I below.
EXAMPLE 6:
Selective complexing and extracting of uranium in urine
In this example, the uranium present at a concentration of 5.10-6 g/1 in urine
is fixed by means of the calixarenes of the invention.
For this experiment, use is made of 1 g of supported liquid membrane from
example 3 packaged in a column.
A preliminary stage of mineralization of the urine is carried out by heating
using microwave radiation. The mineralization residue is taken up in a 2M
ITNO3 solution and then the pH of the solution is adjusted to 4 before
passing through the column.
The conditioning, fixing, rinsing and elution stages are identical to those
described in example 4. The uranium is measured and the results are
expressed as above.
The results obtained are given in table I below.
EXAMPLE 7:
Selective complexing and extracting of plutonium
In this example, the plutonium present at a concentration of 10-10 mol.l-1 in a
0.04 mol.l-1 aqueous NaNO3 solution simulating the urinary medium and
adjusted to pH = 4 is fixed by means of the calixarenes of the invention.
For this experiment, use is made of 100 mg of support material from
example 1-5 packaged in a column.

- 3 9 -
The conditioning, fixing, rinsing and elution stages are identical to those
described in example 4. The plutonium is measured by alpha spectrometry
or by mass spectrometry (ICP-MS) in each solution at the column bottom.
The results of the measurements make it possible to calculate the fixing
vieki and the elution vield for plutonium.
The resuhs obtained are given \v. table I helow.
Table I: Fixing and elution yields (%)

EXAMPLE 8:
Supported liquid membrane comprising l-hydroxy-3,5-dimethoxy-
2,4,6-tri(carboxylic acid)-p-tert-biltylcalix[6]arene (RM -=1.174.4)

5.03 g of product (white powder) obtained in example 1-3, during the
implementation of a second test identical to the preceding one, (4.00 mmol)

- 40 -
and 150 ml of ethanol are introduced into a 250 ml glass reactor equipped
with a condenser. A solution prepared beforehand (and maintained at +5°C)
of potassium hydroxide flakes (12 g at 100%, i.e. 214 mmol) in 150 ml of
water is added all at once to the reactor. The reaction medium is brought to
reflux for 4 hours while bubbling nitrogen through.
25 ml of 12M HC1 are slowly added after cooling the reaction mass to 20°C.
The expected product precipitates in the form of a white solid. The
suspension is subsequently filtered and the solid is washed with 8 times
50 ml of water and then 2 times 50 ml of ethanol. The solid is subsequently
dried at 40°C under vacuum to constant weight.
4.65 g of white solid are obtained after drying at 40°C under vacuum to
constant weight (yield = 99%).
The proton NMR spectrum at 300 MHz in CDC13 gives the following
chemical shifts:
6.86 ppm (s, 13H, ArH meta + OH phenol), 3.95 ppm (s, 6H,
ArCH2COOH), 3.73 ppm (broad s, 6H, methoxy), 1.12 ppm (s, 27H, tert-
butyl para OCH2COOH), 1.09 ppm (s, 27H, tert-butyl para OCH3).
2 g of resin, Macroprep epoxy, from BioRad, particle size of 70 to 100 μm,
batch 11/99, are added to the solution prepared beforehand of 12.5 mg,
withdrawn from the 4.65 g of white solid obtained above, dissolved in 20 ml
of dichloromethane and 1.12 ml of 1-heptanol. The suspension is gently
evaporated at ambient temperature to constant weight: a white solid is
obtained.
Weight obtained: 2.2 g
Selective complexing and extracting of uranium

- 41 -
In this example, the uranium present at a concentration of 10" mol.l-1 in a
0.04 mol.l-1 aqueous NaNO3 solution simulating the urinary medium and
adjusted to pH = 4 is fixed by means of the calixarenes of the invention.
For this experiment, use is made of 1 g of supported liquid membrane
obtained above packaged in a column.
The conditioning, fixing, rinsing and elution stages are identical to those
described in example 4. The uranium is measured and the results are
expressed as in the preceding examples.
The results obtained are given in table II below.
Selective complexing and extracting of thorium
In this example, the thorium present at a concentration of 10-8 mol.l-1 in a
0.04 mol.l"1 aqueous NaNO3 solution simulating the urinary medium and
adjusted to pH = 3 is fixed by means of the calixarenes of the invention.
For this experiment, use is made of 1 g of the supported liquid membrane
obtained above packaged in a column.
The conditioning, fixing, rinsing and elution stages are identical to those
described in example 4, the conditioning and rinsing solutions being
adjusted to pH 3. The thorium is measured by alpha spectrometry or by mass
spectrometry (ICP-MS) in each solution at the column bottom and the
results are expressed as in the preceding examples.
The results obtained are given in table II below.
Table II: Fixing and elution yields (%)

Example 8 Fixing yield (%) Elution yield (%)
Uranium 99+1 73 ±8
Thorium 60+1 70 ±1

- 42 -
We claim:
1. A para-tert-butylcalix[6]arene of formula (IA) or (IB)

where R1, R3 and R5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30. carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation,

- 43 -
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses;
with the following conditions:
R1, R3 and R5 not simultaneously representing CH3 in (IA) and (IB),
R1, R3 and R5 not simultaneously representing CH2COOH in (IA), and
R1, R3 and R5 not simultaneously representing CH2CONHOH in (IB).
2. The para-tert-butylcalix[6]arene as claimed in claim 1, characterized
in that two from R1, R3 and R5 represent hydrogen or methyl, the third
being chosen from (vi) a polymer chosen from the group comprising of
polystyrenes, copolymers of chloro- and/or bromomethylstyrene and of
divinylbenzene, polyethers, polyacrylamides, poly(glycidyl mefhacrylate)s,
dextrans and agaroses.

- 4 4 -
3. The para-tert-butylcalix[6]arene as claimed in claim 1, characterized
in that R1, R3 and R5 are identical.
4. The para-tert-butylcalix[6]arene as claimed in claim 1, characterized
in that Rl, R3 and R5 represent a hydrogen.
5. A supported liquid membrane comprising a para-tert-
butylcalix[6]arene of formula (IA) or (IB)

where Rl, R3 and R5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,

- 45 -
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30, carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation,
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses;
said product of formula (IA) or (IB) being dissolved in an organic solvent
and absorbed on a support.
6. A supported liquid membrane comprising a para-tert-
butylcalix[6]arene as claimed in any one of claims 2 to 4.
7. The supported liquid membrane as claimed in claim 5 or 6,
characterized in that the organic solvent exhibits a boiling point of greater
than 60°C and is chosen from the group comprising in particular toluene,

- 46 -
xylene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, 1,4-
diisopropylbenzene, hexylbenzene, kerosene, tetrahydropyran, 1,2,3,4-
tetrahydronaphthalene, pentanol and higher homologous alcohols, glycols
and their ethers, such as, for example, diethylene glycol dibutyl ether, esters,
such as methyl benzoate, ethers, such as ortho-nitrophenyl pertyl ether or
nitrophenyl octyl ether, and their mixtures.
8. The supported liquid membrane as claimed in any one of claims 5 to
7, characterized in that the support is a support of inorganic origin, chosen
from the group comprising of a silica gel, oxides, such as alumina, zirconia
and titanium oxide, or of organic origin, chosen from the group comprising
of polystyrene/divinylbenzenes, polyethers, polyacrylamides and
poly(glycidyl methacrylate)s, or of organo-inorganic origin, chosen from the
group comprising of silica/dextran and hydroxyapatite/agarose composites,
and their mixtures.
9. The supported liquid membrane as claimed in any one of claims 5 to
8, characterized in that the support is a particulate support, the particle size
of which varies between 10 nm and 10 mm, preferably between 10 and 50
microns, and the pore diameter of which varies between 10 and 5000 A,
preferably between 100 and 500 A.
10. A support material which is a para-tert-butylcalix[6]arene of formula
(IIA) or (IIB)

- 47 -

where R'1, R'3 and R'5, which are identical or different, represent, each
independently:
(i) a hydrogen or halogen atom,
(ii) an acetyl, amino, phosphate, nitro, sulfate, carboxyl, carboxylic,
thiocarboxyl, carbamate or thiocarbamate radical,
(iii) an optionally substituted linear or branched alkyl having 1 to 60,
preferably 1 to 30, carbon atoms which optionally exhibits at least
one ethylenic or acetylenic unsaturation,
(iv) an optionally substituted cycloalkyl having from 3 to 12 carbon
atoms which optionally exhibits at least one ethylenic or
acetylenic unsaturation,
(v) an optionally substituted aryl, an optionally substituted naphthyl,
an optionally substituted aryl(C1-C30 alkyl) or an optionally
substituted (C1-C30 alkyl)aryl;

- 48 -
it being possible for the radicals (ii) to (v) to be substituted by halogen
atoms, organometallic compounds, alcohol, amine, carboxylic, sulfonic,
sulfuric, phosphoric, phosphonic or hydroxamic acid or ester, carbamate,
thiocarbamate, ether, thiol, epoxide, thioepoxide, isocyanate or
isothiocyanate functional groups or it being possible for a carbon of these
radicals to be replaced by a nitrogen, sulfur, phosphorus, oxygen, boron or
arsenic heteroatom;
(vi) a polymer chosen from the group comprising of polystyrenes,
copolymers of chloro- and/or bromomethylstyrene and of divinylbenzene,
polyethers, polyacrylamides, poly(glycidyl methacrylate)s, dextrans and
agaroses;
(vii) -SPACER-SUPPORT,
the SPACER being a divalent radical chosen from the group comprising of
C1-C60, preferably C1-C30, alkylenes, (C1-C60 alkyl)arylenes, aryl(C1-C60
alkylenes) and aryl(C1-C60 alkyl)aryls, it being possible for the divalent
radical to be substituted by halogen atoms, organometallic compounds,
alcohol, amine, acid, ester, carbamate, thiocarbamate, ether, thiol, epoxide,
thioepoxide, isocyanate or isothiocyanate functional groups or it being
possible for a carbon of this divalent radical to be replaced by a nitrogen,
sulfur, phosphorus, oxygen, boron or arsenic heteroatom;
the SUPPORT being chosen from supports of inorganic or organic or
organo-inorganic origin, preferably particulate supports, the particle size of
which varies between 10 nm and 10 mm, preferably between 10 and 50
microns, and the pore diameter of which varies between 10 and 5000 A,
preferably between 100 and 500 A;
provided that at least one of R' 1, R'3 or R'5 is a (vi) or (vii) group.
11. The support material as claimed in claim 10, characterized in that the
SUPPORT is a support of inorganic origin, chosen from the group

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comprising of silica gels, oxides, such as alumina, zirconia and titanium
oxide, or of organic origin, chosen from the group comprising of
polystyrene/divinylbenzenes, polyethers, polyacrylamides and poly(glycidyl
methacrylate)s, or of organo-inorganic origin, chosen from the group
comprising of silica/dextran or hydroxyapatite/agarose composites.
12. The use of a supported liquid membrane as claimed in any one of
claims 5 to 9 and/or of a support material as claimed in claim 10 or 11 for
the selective complexing and the analysis of the elements uranium,
americium and plutonium or other radioelements in their cationic form.
13. The use of a supported liquid membrane as claimed in any one of
claims 5 to 9 and/or of a support material as claimed in claim 10 or 11 for
removing, from a mixture of at least two constituents chosen from the group
comprising of organic, inorganic or organo-inorganic molecules, at least a
portion of one of these constituents or for separating said constituents by a
chromatographic method.
Dated this 15th Day of November 2007.

The invention relates to novel p-tert-butylcalix [6] arenas of formulae (IA) and
(IB) with carboxylic or hydroxyamino triacidic functions in positions 2, 4 and 6,
and other functions in positions 1, 3 and 5, supported liquid membranes and
support materials comprising the above and the uses thereof.