Synthesis of noncyclic carriers for cerium ion transport through polymer inclusion membrane

Article abstract of DOI:10.1246/cl.2005.1636

Noncyclic ionophores having both diphenylphosphinyl methylcarbamoyl and N,N-di(2-ethylhexyl)carbamoylmethoxy groups were synthesized for cerium ion transport through polymer inclusion membrane. The derivative of 3-aminopropanol having these groups was fou

Full text of DOI:10.1246/cl.2005.1636

1636
Chemistry Letters Vol.34, No.12 (2005)
Synthesis of Noncyclic Carriers for Cerium Ion Transport through Polymer Inclusion Membrane
Kazuhisa Hiratani,ꢀ Samuel Puriyantoro Kusumocahyo,y Naohiro Kameta, Kenta Sugaya,
Toshio Shinbo,y and Toshiyuki Kanamoriꢀy
Department of Applied Chemistry, Utsunomiya University, 7-1-2 Youtou, Utsunomiya 321-8585
yNational Institute of Advanced Industrial Science and Technology,
AIST Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565
(Received June 29, 2005; CL-050830)
Noncyclic ionophores having both diphenylphosphinyl
methylcarbamoyl and N,N-di(2-ethylhexyl)carbamoylmethoxy
groups were synthesized for cerium ion transport through poly-
mer inclusion membrane. The derivative of 3-aminopropanol
having these groups was found to be an excellent carrier over
2-aminoethanol derivatives.
having both diphenylphosphoryl methylcarbamoyl and N,N-
di(2-ethylhexyl or n-octyl)carbamoylmethoxy groups. They
were confirmed by NMR, ESI-mass, Precise Mass, and IR.6
In order to investigate the effect of the structure, some alkyl-
ene groups and ortho-phenylene group were introduced as a
spacer between diphenylphosphorylmethylcarbamoyl and N,N-
di(2-ethylhexyl or n-octyl)carbamoylmethoxy groups.
Cellulose triacetate was used to form the PIM and to support
ligand in solvent (2-nitrophenyl n-octyl ether/ NPOE).7 The
PIM was prepared using a procedure, which is described in detail
elsewhere.8 We tried to transport cerium ion by using the PIMs
containing ligands 1–4 newly synthesized. In the initial condi-
tions, feed phase contains 200 ppm cerium nitrate 0.05 M nitric
acid, and 2.95 M of sodium nitrate, on the other hand, strip phase
contains distilled and deionized water. Both phases were stirred
with stirrer bar at 600 rpm at 40 ꢁC. The details of the transport
apparatus and the experimental procedure are described else-
where.8 Figure 1 shows an example of transport of cerium ion
through PIMs containing ligands 1–4 with time. Under these
conditions, more than 90% of cerium ion in the feed phase can
be transported into the strip phase with ligands except 1 within
3 h. Ligand 4 is the best carrier among them. The transport abil-
ity of dimethyl-substituted ligand 3 is better than that of ligand 2,
probably because its lypophilicity increases and freedom of
rotation of C–C bond decreases. Trimethylene derivative 4 can
transport cerium ion very effectively as shown in Figure 1. Tri-
methylene chain might be advantageous to make 2:1 complex
with cerium ions because the two functional groups can smooth-
ly work as chelating agent. On the other hand, the transport abil-
ity of phenylene derivative 1 drastically decreases compared
Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine
oxide (CMPO),1 N,N,N0,N0-tetraoctyl-3-oxapentanediamide
(TODGA),2 and macrocyclic derivatives based on calixarenes,3
resorcinarenes,4 etc. have been reported to be excellent extrac-
tants and carriers for lanthanoid and actinoid metal ions. They
can be used for the separation of valuable metal ions and radio-
active wasted actinoid ions.2 If they are available not only as ex-
tractants but also carriers for the separation technology, they
could be utilized for effective separation processes such as treat-
ment of radioactive wastewater. In particular, separation through
liquid membranes does not need to use a large amount of iono-
phores (carriers) for the separation of the target ions. Therefore,
synthesis of carriers, which can be used in the membrane sys-
tems, is one of the important goals.
In this paper, we report the synthesis of a new hybrid-type
carrier having not only CMPO moiety but also TODGA moiety
partly because both carbamoylmethylphosphine oxide of CMPO
and oxamethylamide of TODGA have a strong coordinative
ability toward lanthanoid and actinoid ions, and the transport
behavior through polymer inclusion membranes (PIM)5 using
them as carriers. Scheme 1 shows the reaction process. That
is, !-aminoalcohol protected by benzaldehyde reacts with N,N-
di(2-ethylhexyl or n-octyl)carbamoylmethyl chloride in DMF
to give N,N-di(2-ethylhexyl)carbamoyl-methoxyalkylamine
derivatives after deprotection of benzaldehyde. The mixture
of amine derivatives and p-nitrophenyl (diphenylphosphinyl)-
acetate3b were stirred in dry and ethanol-free chloroform at
45 ꢁC for three days to result in the formation of ionophores
1
0.8
0.6
0.4
0.2
0
Ph
Ph
N
O
N
NH2
OH
Ph-CHO
1) NaH
2)
X
X
X
NR2
NR2
OH
Cl
O
O
O
O
P
Ph
Ph
Ph
Ph
HN
P
O2
N
O
NH2
H+
0
50
100
150
200
250
300
X
O
O
X
O
NR2
O
NR2
Time [min]
O
O
Me
Figure 1. Transport of Ce(III) through PIM with carriers, 1–4;
conditions: membrane thickness 49 mm, Feed: 200 ppm Ce-
(NO3)3 in 0.05 M HNO3/2.95 M NaNO3, Strip: water, Temp:
Me
X
:
R = 2-Ethylhexyl
or n-octyl
1
2
3
4
40 ꢁC, Stirring: 600 rpm. 1 :
symbols: strip, open symbols: feed).
, 2 :
, 3 :
, 4 :
(filled
Scheme 1. Reaction process of synthesis of carriers, 1–4.
Copyright ꢀ 2005 The Chemical Society of Japan

Chemistry Letters Vol.34, No.12 (2005)
1637
This work was financially supported by the Budget for
Nuclear Research of the Ministry of Education, Culture, Sports,
Science and Technology, Japan, based on the screening and
counseling by the Atomic Energy Commission.
1
0.8
0.6
0.4
0.2
0
References and Notes
1
a) E. P. Horwitz, K. A. Martin, H. Diamond, and L. Kaplan,
Solvent Extr. Ion Exch., 4, 449 (1986). b) W. W. Schulz and
E. P. Horwitz, Sep. Sci. Technol., 23, 1191 (1988). c) H.
Naganawa, H. Suzuki, and S. Tachimori, Phys. Chem. Chem.
Phys., 2, 3247 (2000). d) H. Boerringter, T. Tomasberger,
A. S. Booij, W. Verboom, D. N. Reinhoudt, and F. de Jong,
J. Membr. Sci., 165, 273 (2000).
0
50
100
150
200
250
300
Time [min]
2
3
a) H. Stephan, K. Gloe, J. Beger, and P. Muehl, Solvent Extr.
Ion Exch., 9, 459 (1991). b) H. Narita, T. Yaita, K. Tamura,
and S. Tachimori, Radiochim. Acta, 81, 223 (1998). c) Y.
Sasaki, Y. Sugo, S. Suzuki, and S. Tachimori, Solvent Extr.
Ion Exch., 19, 91 (2001).
a) F. Arnaud-Neu, V. Boehmer, J.-F. Dozol, C. Gruetter,
R. A. Jakobi, D. Kraft, O. Mauprivez, H. Rouquette, M.-J.
Schwing-Weill, N. Simon, and W. Vogt, J. Chem. Soc.,
Perkin Trans. 2, 1966, 1175. b) M. R. Yaftian, M. Burgard,
C. B. Dieleman, and D. Matt, J. Membr. Sci., 144, 57 (1998).
H. Berrigter, W. Verboom, and D. N. Reinhoudt, J. Org.
Chem., 62, 7148 (1997).
Figure 2. Transport of Ce(III) through PIM with carriers, 4 and
, TODGA :
TODGA; conditions: same as Figure 1. 4 :
(filled symbols: strip, open symbols: feed).
with ligand 2. Forming intermolecular, stable complex with ce-
rium ion, the rigid benzene part between two functional groups
would work disadvantageously.
The transport ability of 4 was compared with TODGA,2
which is one of the best potent candidates for lanthanoid or
actinoid extractants and carriers, under the same conditions.
Figure 2 shows the transport behaviors of two carriers. Ligand
4 surpasses TODGA in the transport ability for cerium ion.
Carrier 4 should also be one of the most potent carriers for
lanthanoid ions through polymer inclusion membranes.
In the membrane system (PIM), these compounds could act
as a tetradentate, otherwise at least tridentate complexing agent.
Although ESI mass spectroscopy of the mixture of these com-
pounds with cerium nitrate in NPOE was measured, any mass
number of the complex with cerium ion was not clearly detected
under the same conditions (40 eV, positive mode, in aceto-
nitrile). However, in FAB mass spectroscopy of the same mix-
ture (matrix: 3-nitrobenzyl alcohol; ionization mode: positive),
mass number of 1461.3 due to the 2:1 complex, [(ligand 4)2 +
Ce(NO3)2]þ (calcd 1460.7) was detected. CMPO was reported
to make 2:1 complex with lanthanoid or actinoid ions in the ex-
traction systems,9 whereas TODGA makes 2:1 or 3:1 complex
with those metal ions.2b These results suggest that ligand 4 might
form 2:1 complex with cerium(III) ion as illustrated in Figure 3.
Thus, the newly prepared hybrid-type carriers having both
properties of CMPO and TODGA can work as excellent carriers
of cerium(III) ion in polymer inclusion membrane (PIM) system.
Further investigation on the synthesis of new carriers is now in
progress.
4
5
6
M. Sugiura, M. Kikkawa, and S. Urita, J. Membr. Sci., 42, 47
(1989).
Only 1 has n-octyl groups as substituent R. Selected data for
1
carriers 1–4: 1: H NMR (CDCl3, ppm) 0.89 (t, 6H, CH3),
1.2 (broad, 20H, CH2), 1.5 (m, 4H, CH2), 2.24 (s, 3H, Ar-
CH3), 3.26 (m, 4H, N-CH2), 3.54 and 3.59 (s, 2H, P-CH2-
CO), 4.72 (s, 2H, CO-CH2-O), 6.75 (d, 1H, Ar-H), 6.78 (s,
1H, Ar-H), 7.5 (m, 6H, Ar-H), 7.8 (m, 4H, Ar-H), 8.08 (d,
1H, Ar-H), 9.92 (s, 1H, NH); Precise Ms: Calcd: 646.39,
Found: 646.396. 2: 1H NMR (CDCl3, ppm) 0.89 (t, 12H,
CH3), 1.26 (broad, 16H, CH2), 1.6 (m, 2H, CH), 3.05 (d,
2H, N-CH2), 3.40 (m, 2H, N-CH2), 3.36 and 3.40 (s, 2H,
P-CH2-CO), 4.13 (s, 2H, CO-CH2-O), 7.5 (m, 6H, Ar-H),
7.7 (m, 4H, Ar-H), 7.9 (broad, 1H, N-H); Precise Ms: Calcd:
584.37, Found: 584.372. 3: 1H NMR (CDCl3, ppm) 0.90 (m,
12H, CH3), 1.18 (s, 6H, CH3), 1.27 (broad, 16H, CH2), 1.64
(m, 2H, CH), 3.05 (d, 2H, N-CH2), 3.32 (m, 2H, N-CH2),
3.32 and 3.37 (s, 2H, P-CH2-CO), 4.13 (s, 2H, CO-CH2-
O), 7.46 (m, 6H, Ar-H), 7.84 (m, 4H, Ar-H), 8.05 (s, 1H,
N-H); Precise Ms: Calcd: 612.41, Found: 612.399. 4:
1H NMR (CDCl3, ppm) 0.89 (m, 12H, CH3), 1.26 (broad,
16H, CH2), 1.64 (m, 2H, CH), 1.65 (m, 2H, CH2), 3.07 (d,
2H, N-CH2), 3.24 (m, 2H, NCH2), 3.31 (t, 2H, N-CH2),
3.35 and 3.40 (s, 2H, P-CH2-CO), 3.42 (t, 2H, O-CH2),
4.11 (s, 2H, CO-CH2-O), 7.5 (m, 6H, Ar-H), 7.8 (m, 4H,
Ar-H), 7.85 (s, 1H, N-H); Precise Ms: Calcd: 598.39, Found:
598.387.
Ph
Ph
H
N
3+
3+
P
O
Ce
3 NO
Ce
3 NO
N
_
O
_
O
3
O
O
N
3
3+
7
8
T. Shinbo, T. Yamaguchi, H. Yanagishita, K. Sakaki, D.
Kitamoto, and M. Sugiura, J. Membr. Sci., 84, 241 (1993).
S. P. Kusumocahyo, T. Kanamori, K. Sumaru, S. Aomatsu,
H. Matsuyama, M. Teramoto, and T. Shinbo, J. Membr.
Sci., 244, 251 (2004).
Ce
O
O
O
N
H
P
Ph
Ph
_
3
3 NO
9
a) K. A. Martin, E. P. Horwitz, and J. R. Ferraro, Solvent
Extr. Ion Exch., 4, 1149 (1986). b) S. D. Baker, B. J.
Mincher, D. H. Meikrantz, and J. R. Berreth, Solvent Extr.
Ion Exch., 6, 1049 (1988).
(Polymer Inclusion Membrane)
(Feed)
(Strip)
Figure 3. Postulated 2:1 complexation of 4 with cerium(III) ion
in the transport through PIM.
Published on the web (Advance View) November 12, 2005; DOI 10.1246/cl.2005.1636