5
F. W. Lewis et al.
Letter
Synlett
The Chemistry of the Actinide and Transactinide Elements; Vol. 1;
Katz, J. J.; Morss, L. R.; Edelstein, N. M.; Fuger, J., Eds.; Springer:
Dordrecht, 2006, 2622.
Madic, C. Dalton Trans. 2006, 1645. (c) Trumm, S.; Lieser, G.;
Foreman, M. R. S.; Panak, P. J.; Geist, A.; Fanghänel, T. Dalton
Trans. 2010, 39, 923. (d) Harwood, L. M.; Lewis, F. W.; Hudson,
M. J.; John, J.; Distler, P. Solvent Extr. Ion Exch. 2011, 29, 551.
(e) Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Distler, P.; John,
J.; Stamberg, K.; Núñez, A.; Galán, H.; Espartero, A. G. Eur. J. Org.
Chem. 2012, 1509.
(3) Salvatores, M.; Palmiotti, G. Prog. Part. Nucl. Phys. 2011, 66, 144.
(4) Seaborg, G. T. Radiochim. Acta 1993, 61, 115.
(5) (a) Choppin, G. R. J. Alloys Compd. 1995, 223, 174. (b) Choppin,
G. R. J. Alloys Compd. 2002, 344, 55. (c) Kaltsoyannis, N. Inorg.
Chem. 2013, 52, 3407. (d) Neidig, M. L.; Clark, D. L.; Martin, R. L.
Coord. Chem. Rev. 2013, 257, 394.
(6) (a) Kolarik, Z. Chem. Rev. 2008, 108, 4208. (b) Lewis, F. W.;
Hudson, M. J.; Harwood, L. M. Synlett 2011, 2609. (c) Hudson, M.
J.; Harwood, L. M.; Laventine, D. M.; Lewis, F. W. Inorg. Chem.
2013, 52, 3414. (d) Panak, P. J.; Geist, A. Chem. Rev. 2013, 113,
1199. (e) Hudson, M. J.; Lewis, F. W.; Harwood, L. M. Strategies
and Tactics in Organic Synthesis; Vol. 9; Harmata, M., Ed.; Else-
vier: Amsterdam, 2013, 177.
(7) Geist, A.; Hill, C.; Modolo, G.; Foreman, M. R. St. J.; Weigl, M.;
Gompper, K.; Hudson, M. J.; Madic, C. Solvent Extr. Ion Exch.
2006, 24, 463.
(8) (a) Magnusson, D.; Christiansen, B.; Foreman, M. R. S.; Geist, A.;
Glatz, J.-P.; Malmbeck, R.; Modolo, G.; Serrano-Purroy, D.; Sorel,
C. Solvent Extr. Ion Exch. 2009, 27, 97. (b) Aneheim, E.; Ekberg,
C.; Fermvik, A.; Foreman, M. R. St. J.; Retegan, T.; Skarnemark, G.
Solvent Extr. Ion Exch. 2010, 28, 437. (c) Aneheim, E.; Ekberg, C.;
Fermvik, A.; Foreman, M. R. St. J.; Grűner, B.; Hájková, Z.;
Kvičalová, M. Solvent Extr. Ion Exch. 2011, 29, 157. (d) Wilden,
A.; Schreinemachers, C.; Sypula, M.; Modolo, G. Solvent Extr. Ion
Exch. 2011, 29, 190. (e) Wilden, A.; Modolo, G.;
Schreinemachers, C.; Sadowski, F.; Lange, S.; Sypula, M.;
Magnusson, D.; Geist, A.; Lewis, F. W.; Harwood, L. M.; Hudson,
M. J. Solvent Extr. Ion Exch. 2013, 31, 519.
(9) (a) Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Drew, M. G. B.;
Desreux, J. F.; Vidick, G.; Bouslimani, N.; Modolo, G.; Wilden, A.;
Sypula, M.; Vu, T.-H.; Simonin, J.-P. J. Am. Chem. Soc. 2011, 133,
13093. (b) Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Drew, M.
G. B.; Hubscher-Bruder, V.; Videva, V.; Arnaud-Neu, F.;
Stamberg, K.; Vyas, S. Inorg. Chem. 2013, 52, 4993. (c) Afsar, A.;
Harwood, L. M.; Hudson, M. J.; Distler, P.; John, J. Chem.
Commun. 2014, 50, 15082.
(16) (a) Burnett, C. A.; Lagona, J.; Wu, A.; Shaw, J. A.; Coady, D.;
Fettinger, J. C.; Day, A. I.; Isaacs, L. Tetrahedron 2003, 59, 1961.
(b) Yin, G.; Wang, Z.; Chen, Y.; Wu, A.; Pan, Y. Synlett 2006, 49.
(c) Li, Y.; Yin, G.; Guo, H.; Zhou, B.; Wu, A. Synthesis 2006, 2897.
(d) Hu, S.-L.; She, N.-F.; Yin, G.-D.; Guo, H.-Z.; Wu, A.-X.; Yang,
C.-L. Tetrahedron Lett. 2007, 48, 1591. (e) Gao, M.; Cao, L.; Wang,
Z.; Sun, J.; She, N.; Wu, A. Synlett 2009, 315. (f) Cao, L.; Ding, J.;
Wang, J.; Chen, Y.; Gao, M.; Xue, W.; Wu, A. Synlett 2010, 2553.
(g) Li, L.; She, N.-F.; Fei, Z.; So, P.-K.; Wang, Y.-Z.; Cao, L.-P.; Wu,
A.; Yao, Z.-P. J. Fluoresc. 2011, 21, 1103.
(17) Khurana, J. M.; Kandpal, B. M. Tetrahedron Lett. 2003, 44, 4909.
(18) Pabst, G. R.; Pfüller, O. C.; Sauer, J. Tetrahedron 1999, 55, 5047.
(19) A BTP ligand with ester groups attached to C6 of the triazine
rings was reported previously, see: Gehre, A.; Stanforth, S. P.;
Tarbit, B. Tetrahedron 2009, 65, 1115.
(20) Synthesis of BTBP 11: The starting material 10 (0.40 g, 0.664
mmol) was dissolved in THF (90 mL) and a solution of NaOH
(0.133 g, 5 equiv) in MeOH (30 mL) was added. The flask was
heated under reflux for 3 h. The flask was allowed to cool to r.t.
and the insoluble solid was filtered and washed successively
with MeOH (40 mL), acetone (10 mL) and CH2Cl2 (10 mL). The
solid was allowed to dry in air to afford the novel BTBP 11 as a
yellow solid (0.35 g, 92%); mp above 300 °C (from MeOH). 1H
NMR (400.1 MHz, D2O): δ = 8.22 (t, J = 7.9 Hz, 2 H, 4-H, 4′-H),
8.55 (dd, J = 7.9, 0.8 Hz, 2 H, 5-H, 5′-H), 8.57 (dd, J = 7.9, 0.8 Hz, 2
H, 3-H, 3′-H). 13C NMR (100.6 MHz, D2O): δ = 124.9 (C-3, C-3′),
125.0 (C-5, C-5′), 139.6 (C-4, C-4′), 151.3 (2 × quat), 152.8 (2 ×
quat), 154.6 (2 × quat), 155.7 (2 × quat), 161.7 (2 × quat), 169.4
(2 × quat), 169.8 (2 × quat). HRMS (CI, H2O; as tetracarboxylic
acid): m/z [M+ H] + for C20H10N8O8: 491.0699; found: 491.0683.
Anal. Calcd for C20H6N8O8Na4: C, 41.54; H, 1.05; N, 19.37. Found:
C, 41.22; H, 1.37; N, 18.98.
(10) (a) Weaver, B.; Kappelmann, F. A. J. Inorg. Nucl. Chem. 1968, 30,
263. (b) Nilsson, M.; Nash, K. L. Solvent Extr. Ion Exch. 2007, 25,
665. (c) Nilsson, M.; Nash, K. L. Solvent Extr. Ion Exch. 2009, 27,
354. (d) Nash, K. L. Solvent Extr. Ion Exch. 2015, 33, 1.
(21) (a) Sasaki, Y.; Sugo, Y.; Suzuki, S.; Tachimori, S. Solvent Extr. Ion
Exch. 2001, 19, 91. (b) Modolo, G.; Asp, H.; Schreinemachers, C.;
Vijgen, H. Solvent Extr. Ion Exch. 2007, 25, 703. (c) Modolo, G.;
Asp, H.; Vijgen, H.; Malmbeck, R.; Magnusson, D.; Sorel, C.
Solvent Extr. Ion Exch. 2008, 26, 62.
(22) Under these conditions, extraction of Am(III) and Eu(III) into
the organic phase by TODGA is more thermodynamically
favored than back-extraction into the aqueous phase. The sul-
fonated ligands 4–6 are also unable to strip Am(III) from the
organic phase at this pH.
(11) Geist, A.; Müllich, U.; Magnusson, D.; Kaden, P.; Modolo, G.;
Wilden, A.; Zevaco, T. Solvent Extr. Ion Exch. 2012, 30, 433.
(12) Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Geist, A.;
Kozhevnikov, V. N.; Distler, P.; John, J. Chem. Sci. 2015, 6, 4812.
(13) (a) Ruff, C. M.; Müllich, U.; Geist, A.; Panak, P. J. Dalton Trans.
2012, 41, 14594. (b) Carrott, M.; Geist, A.; Hères, X.; Lange, S.;
Malmbeck, R.; Miguirditchian, M.; Modolo, G.; Wilden, A.;
Taylor, R. Hydrometallurgy 2015, 152, 139. (c) Wilden, A.;
Modolo, G.; Kaufholz, P.; Sadowski, F.; Lange, S.; Sypula, M.;
Magnusson, D.; Müllich, U.; Geist, A.; Bosbach, D. Solvent Extr.
Ion Exch. 2015, 33, 91.
(23) Trumm, S.; Wipff, G.; Geist, A.; Panak, P. J.; Fanghänel, T. Radio-
chim. Acta 2011, 99, 13.
(24) (a) Lan, J.-H.; Shi, W.-Q.; Yuan, L.-Y.; Zhao, Y.-L.; Li, J.; Chai, Z.-F.
Inorg. Chem. 2011, 50, 9230. (b) Lan, J.-H.; Shi, W.-Q.; Yuan, L.-
Y.; Feng, Y.-X.; Zhao, Y.-L.; Chai, Z.-F. J. Phys. Chem. A 2012, 116,
504. (c) Lan, J.-H.; Shi, W.-Q.; Yuan, L.-Y.; Li, J.; Zhao, Y.-L.; Chai,
Z.-F. Coord. Chem. Rev. 2012, 256, 1406.
(14) Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Müllich, U.; Geist, A.
Chem. Commun. 2015, 51, 9189.
(15) See for example: (a) Drew, M. G. B.; Foreman, M. R. S. J.; Hill, C.;
Hudson, M. J.; Madic, C. Inorg. Chem. Commun. 2005, 8, 239.
(b) Foreman, M. R. S.; Hudson, M. J.; Drew, M. G. B.; Hill, C.;
© Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, 1–5