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Citation: Lewis, Frank, Harwood, Laurence M., Hudson, Michael J., Distler, Petr, John, Jan, Stamberg, Karel, Nunez, Ana, Galan, Hitos and Espartero, Amparo G

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Citation: Lewis, Frank, Harwood, Laurence M., Hudson, Michael J., Distler, Petr, John, Jan, Stamberg, Karel, Nunez, Ana, Galan, Hitos and Espartero, Amparo G View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Northumbria Research Link Citation: Lewis, Frank, Harwood, Laurence M., Hudson, Michael J., Distler, Petr, John, Jan, Stamberg, Karel, Nunez, Ana, Galan, Hitos and Espartero, Amparo G. (2012) Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separations in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design. European Journal of Organic Chemistry, 8. pp. 1509- 1519. ISSN 1434-193X Published by: Wiley-Blackwell URL: http://dx.doi.org/10.1002/ejoc.201101576 This version was downloaded from Northumbria Research Link: http://nrl.northumbria.ac.uk/10884/ Northumbria University has developed Northumbria Research Link (NRL) to enable users to access the University’s research output. Copyright © and moral rights for items on NRL are retained by the individual author(s) and/or other copyright owners. Single copies of full items can be reproduced, displayed or performed, and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided the authors, title and full bibliographic details are given, as well as a hyperlink and/or URL to the original metadata page. The content must not be changed in any way. Full items must not be sold commercially in any format or medium without formal permission of the copyright holder. The full policy is available online: http://nrl.northumbria.ac.uk/policies.html This document may differ from the final, published version of the research and has been made available online in accordance with publisher policies. To read and/or cite from the published version of the research, please visit the publisher’s website (a subscription may be required.) FULL PAPER DOI: 10.1002/ejoc.200((will be filled in by the editorial staff)) Synthesis and Evaluation of Lipophilic BTBP Ligands for An/Ln Separations in Nuclear Waste Treatment: Effect of Alkyl Substitution on Extraction Properties and Implications for Ligand Design Frank W. Lewis,*[a] Laurence M. Harwood,*[a] Michael J. Hudson,[a] Petr Distler,[b] Jan John,[b] Karel Stamberg,[b] Ana Núñez,[c] Hitos Galán[c] and Amparo G. Espartero[c] Keywords: Ligands / Actinides / Lanthanides / Nuclear waste / Extraction Four new 6,6’-bis(1,2,4-triazin-3-yl)-2,2’-bipyridine (BTBP) Quite unexpectedly, both alkyl-substituted ligands 12 and 13 ligands containing either additional alkyl groups on the pyridine showed lower solubilities in certain diluents than the non- rings, or 7-membered aliphatic rings attached to the triazine rings, substituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, have been synthesized, and the effects of additional alkyl alkyl-substitution was found to decrease the rates of metal ion substitution in the 4- and 4’-positions of the pyridine rings on their extraction of the BTBPs in both 1-octanol and cyclohexanone. A extraction properties with Ln(III) and An(III) cations in simulated highly efficient (DAm > 10) and selective (SFAm/Eu > 90) nuclear waste solutions were studied. The speciation of ligand 13 extraction was observed for BTBPs 12 and 13 in cyclohexanone, with some trivalent lanthanide nitrates was elucidated by 1H NMR and for BTBP 13 in 1-octanol in the presence of a phase-transfer titrations and electrospray-ionization mass spectrometry. Whereas agent. The implications of these results for the design of ligand 13 formed both 1:1 and 1:2 complexes with La(III) and improved extractants for radioactive waste treatment are Y(III), only 1:2 complexes were observed with Eu(III) and Ce(III). discussed. ____________ triazin-3-yl)-2,2’-bipyridine (BTBP)[6] ligands, and one member of [a] Department of Chemistry, University of Reading, Whiteknights, [7,8] Reading RG6 6AD, UK the latter family (CyMe4-BTBP 1, Figure 1) is the current Fax: +44 (0) 118 378 6121 benchmark ligand for the SANEX process, as demonstrated on E-mail: [email protected], [email protected] genuine waste fuel solution.[9] The substituted aliphatic rings [b] Department of Nuclear Chemistry, Czech Technical University in present in 1 are designed to confer solubility in suitable solvents Prague, Břehová 7, 115 19 Prague 1, Czech Republic such as 1-octanol, while the absence of benzylic hydrogens Fax: + 420 222 317 626 E-mail: [email protected] enhances the resistance of the ligands to radiolytic degradation [c] Centro de Investigaciones Energéticas, Medio Ambientales y caused by free-radical species.[10] Recently, it has been shown that Tecnológicas (CIEMAT), Avda. Complutense, 40.28040-Madrid, the extraction properties of ligands such as 1 can be improved Spain considerably if the ligand is pre-organized for metal binding with a Fax: + 34 913 460 837 phenanthroline moiety, which locks the ligand into the required cis E-mail: [email protected] [11] Supporting information for this article is available on the WWW conformation. under http://www.eurjoc.org/ or from the author. The tert-butyl-substituted derivative 2[12] (Figure 1) posesses a higher solubility than CyMe4-BTBP 1 in suitable diluents such as Introduction 1-octanol and cyclohexanone,[13] although its solvent extraction kinetics are slower than those of 1. More recently, a symmetrical One of the major goals in the treatment of nuclear waste arising BTP ligand derived from camphor has shown both improved from the PUREX process is the selective removal of the radiotoxic solubility and fast extraction kinetics compared to related BTP minor actinides (Am and Cm) from the lanthanides in a solvent [14] [1] ligands. However, this ligand is susceptible to precipitate extraction process, known as the SANEX process. Once removed, formation in contact with nitric acid solutions of high acidity. A the oxides of these elements may be converted by high-energy high extractant solubility is desirable for the treatment of waste neutrons (transmutation) into less radiotoxic or non-radiotoxic solutions containing high concentrations of metal ions, such as elements, enabling the safer geological disposal of the remaining those produced in the PUREX process.[15] In this study, we have waste, or they may be used as fuel in their own right in the therefore synthesized and evaluated some lipophilic symmetrical proposed Generation IV fast reactors.[2] This strategy, known as BTBP ligands based on CyMe4-BTBP 1 containing either two Partitioning and Transmutation, promises to reduce the additional alkyl groups, or 7-membered aliphatic rings in order to environmental impact and ultimately increase the sustainability of [3] determine the effects of these modifications on the solubilities and nuclear energy. extraction properties of the ligands, and our results are reported herein. A large number of extractants has been proposed and tested in recent years for their ability to extract actinides in the presence of lanthanides from aqueous nitric acid solutions produced during the PUREX reprocessing of nuclear waste.[4] Most promising are the 2,6-bis(1,2,4-triazin-3-yl)pyridine (BTP)[5] and the 6,6’-bis(1,2,4- Submitted to the European Journal of Organic Chemistry 1 R LDA O O O I I OEt EtO OEt N N Et2O N N N N 14 15 N N Na, Me3SiCl toluene 1 R = H 2 R = t-Bu O OSiMe Br2 3 Figure 1. Structures of CyMe4-BTBP 1 and MF2-BTBP 2. O CCl4 OSiMe3 17 16 Results and Discussion Scheme 2. Ligand Synthesis The 4,4’-disubstituted BTBP ligands 12 and 13 were synthesized O O O Na2S.9H2O using the same methodology previously used to synthesize CyMe4- Cl OH RO S OR [7,8] Na2CO3 BTBP 1. Oxidation of the 2,2’-bipyridines 3 and 4 with H O [16,17] 18 2 H2SO4 19 R = H hydrogen peroxide in acetic acid afforded the bis-N-oxides 5 EtOH 20 R = Et and 6[17,18] which were converted to the dicarbonitriles 7[17,19] and [17] Na, Me3SiCl 8 by a Reissert-Henze reaction with trimethylsilyl cyanide and toluene benzoyl chloride in DCM (CAUTION: trimethylsilyl cyanide is a volatile hydrogen cyanide equivalent!). The dicarbonitriles 7 and 8 O OSiMe Br2 3 were treated with hydrazine hydrate in ethanol to generate the S S CCl novel dicarbohydrazonamides 9 and 10 in 81 % and 79 % yields, O 4 OSiMe3 respectively. Finally, condensation of 9 and 10 with 3,3,6,6- tetramethylcyclohexane-1,2-dione 11[20] (which was synthesized by 22 21 a modified procedure)[11,21] furnished the new 4,4’-disubstituted BTBP ligands 12 and 13 (Scheme 1). Scheme 3. R R R R R R The condensation reaction of dicarbohydrazonamide 23 with H O Me SiCN 2 2 3 each of the diketones 17 and 22 failed to generate the N N AcOH N+ + N PhCOCl N N – – O O NC CN corresponding BTBP ligands 24 and 25 in a range of different 3 R = Me 5 R = Me 7 R = Me solvents (THF, dioxane, EtOH, toluene, dibutyl ether, DMSO), and 4 R = t-Bu 6 R = t-Bu 8 R = t-Bu starting materials were recovered in each case. Eventually, we found that the reactions proceeded in pyridine after refluxing for 3 N2H4 EtOH days (Scheme 4). We attribute the reduced reactivity of the 7- O R R 11 R R membered ring diketones 17 and 22 in these reactions to the O differences in the O=C–C=O dihedral angles between these [25b] N N N N diketones and the more reactive 6-membered ring diketone 11. N N Et3N N N 1 dioxane Examination of the H NMR spectrum of the crude products N N H2N NH2 H2N NH2 N N showed the expected resonances of the BTBPs in addition to at 9 R = Me least one other product in each case that could not be identified.
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