ES3009232B2 - TSIL compound, preparation procedure, and procedure for the selective extraction of inner transition elements from s, d, and p-series metals using TSIL compound - Google Patents

Description

[0001] DESCRIPTION

[0002] TSIL compound, preparation procedure and procedure for the selective extraction of inner transition elements from s, d and p series metals using the TSIL compound

[0004] TECHNICAL SECTOR

[0006] The present invention relates to the preparation of a compound called a task-specific ionic liquid (TSIL) with chemical formula (5), which, together with an ionic liquid [CYPHOS NTf2] (6), generates a composition—an extractant mixture (5)+(6)—for use in highly effective selective extraction processes for selectively extracting elements known as inner transition metals (f-block) as opposed to metals of the s, d, and p series of the periodic table. The extraction selectivity of the aforementioned mixture (5)+(6) is much lower or nonexistent compared to the latter.

[0008] Advantageously, once the selective extraction process of the internal transition metals using the extractant mixture (5)+(6) is completed, it is possible to fully recover the complexed metal(s), making it possible to recycle them for later use as an extractant mixture in a new extraction process or cycle.

[0010] This invention has multiple applications in various fields, notably the extraction of the aforementioned elements, which are quite scarce and widely distributed throughout the Earth's crust. Furthermore, it also has significant applications in the fields of nuclear chemistry and nuclear medicine.

[0012] Thus, the present invention relates to the compound TSIL with chemical formula (5), the process for preparing said compound TSIL, as well as the process for selectively extracting inner transition metals (belonging to the two f blocks of the periodic table of elements) from the metals of the s, d and p series, using an extractant mixture (5)+(6) based on the compound TSIL.

[0013] PRIOR ART STATEMENT

[0015] The inner transition elements occupy a position between lanthanum (Z=57) and hafnium (Z=72), and between actinium (Z=89) and rutherfordium (Z=104). The elements following lanthanum are called lanthanides or lanthanoids, while those following actinium are the actinides or actinoids. These elements, also called f-block elements, are characterized by their scarcity and dispersion in the Earth's crust. Separating one of these elements from the other f-block metals and from the s-, d-, and p-block metals is a very difficult, tedious, and economically costly task.

[0017] In general, lanthanides are used as effective catalysts (hard Lewis acids) in industrial-scale chemical processes. However, rare earth elements (REEs) are essential components in over 200 products across a wide range of applications, particularly high-tech consumer products such as mobile phones, computer hard drives, electric and hybrid vehicles, and flat-screen monitors and televisions, as well as in optics, etc. Military and defense applications are highly relevant, as the presence of these elements is crucial in the manufacture of electronic displays, guidance systems, lasers, and radar and sonar systems.

[0019] On the other hand, all actinides are radioactive and release energy through their respective decay chains. Uranium and thorium (naturally occurring) and plutonium (synthetically produced) are the most abundant actinides on Earth. These are used in nuclear reactors, nuclear weapons, and nuclear medicine.

[0021] The methods used to separate and obtain f-block elements free of the remaining s-, d-, and p-series metals are numerous [Jia, J.-P.; Huang, J.-J.; Ma, Z.-L.; Liu, X.-H.; Chen, X.-Y.; Li, J.-T.; He, L.-H.; Zhao, Z.-W. Trans. Nonferrous Met. Soc. China 2020, 30, 3147–3160], and most of them are based on liquid-liquid extraction procedures. Other alternatives exist, such as the recycling mode of the hollow fiber renewal liquid membrane (HFRLM) process [Allahyari, S. A.; Ahmadi, S. J.; Minuchehra, A.; Charkhi, A.RSC Adv.2017, 7, 7413-7423.], a liquid membrane containing N,N,N0,N0-tetraoctyl-3-oxapentanediamide (TODGA) as the extractant [Panja, S.; Mohapatra, P.K.; Tripathi, S.C.; Manchanda V.K.Sep. Sci. Technol.2010,45,1112-1120], including by high-performance liquid chromatography [Telmore, V. M.; Kumar, P.; Jaison, P. G.; Mhatre, A.; Naik, H.J. Radioanal. Nucl. Chem.2017,313,319-326; Friend, M.T.; Parker, T.G.; Mastren, T.; Mocko, V.; Brugh, M.; Birnbaum, E.R.; Fassbender, M.E.J. Chromatogr. A2020,1624,461219].

[0022] Within liquid-liquid extractions, there are processes that use a phosphate buffer [Silva, R. G.; Morais, C. A.; Oliveira, E. D. Miner. Eng. 2019, 134, 402-416], another that consists of a new dispersive liquid-liquid microextraction (DLLME) based on a deep hydrophobic eutectic solvent [Sadeghi, S.; Davami, A.J. Mol. Liq. 2019, 291, 111242], liquid-liquid extraction using fatty acids [Didi, M. A.; Villemin, D.; Abderrahim, O.; Azzouz, A.J. Radioanal. Nucl. Chem.2014,299,1191-1198], through a separation process based on the use of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]acetic acid (POAA) [Su, J.; Xu, R.; Ni, S.; Li, F.; Sun, X.J. Clean. Prod.2020,254,119931], the use of a high-efficiency chelating agent by functionalizing graphene oxide with phenanthroline diamide (GO-PDA) [Li, F.; Yang, Z.; Weng, H.; Chen, G.; Lin, M.; Zhao, C.Chem. Eng. J.

[0023] 2018,332,340-350], using a binary extractor composed of 1,5-bis[o-(dioxyphosphoryl)-petylphenoxy]-3-oxapentane and an amine such as trioctylamine [Safiulina, A. M.; Ivanets, D.V.; Kudryavtsev, E.M.; Baulin, D.V.; Baulin, V.E.; Tsivadze, A. Y. Rus. J. Inorg. Chem.2018,63,1679-1683], N-n-heptylaniline [Pawar, R. R.; Suryavanshi, V.J.; Salunkhe, S.T.; Patil, S.S.; Mulik, G.N.J. Radioanal. Nucl. Chem.2017,311,419-426.], a hexaacetate-calix(6)arene [Swamidoss, C. M. A.; Ramaswamy, K.; Tallam, V.G.Mat. Today: Proceedings2020, 954 957] or a bidentate ligand, 2,3-dihydroxynaphthalene [Tarafder, P. K.; Pradhan, S.K.; Mondal, R.K.J. Radioanal. Nucl. Chem.2016,309,1021-1028].

[0025] The use of ionic liquids (ILs) has been fundamental in many examples of selective chemical separation, and this has also been implemented in this area. Thus, the use of ILs together with extractive ligands is very well documented, for example, amines [Zuo, Y.; Chena, J.; Li, D. Sep. Pur. Tech. 2008, 63, 684-690], 1,3-diketones (separation with SC-CO2) [Fu, J.; Chen, Q.; Sun, T.; Shen, X. Sep. Pur. Tech. 2013, 119, 66-71], N,N-dialkylamides (separation with SC-CO2) [Rao, A.; Tomar, B. S. Sep. Pur. Tech. 2016, 161, 159-164], diglycolamides [Luo, H. M.; Boll, R.A.; Bell, JR; Dai, S.Radiochim. Acta2012,100,771-777], phosphine oxides (separation with oxalic acid) [Sengupta, A.; Singh, M.; Sundarajan, M.; Yuan, L.; Fang, Y.; Yuan, X.; Feng, W. Inor. Chem. Commun.2017,75,33 36; Turanov, A. N.; Karandashev, V.K.; Artyushin, O. I.; Sharova, E.V.; Khvostikov, V. A.Radiochem.2021,63,162-168; Turanov, A. N.; Karandashev, V.K.; Baulin, D.V.; Baulin, V. E. Russ. J. Gen. Chem.2020,90,1012-1019; Turanov A. N.; Karandashev, V.K.; Burmii, Zh, P.; Yarkevich, A. N. Russ. J. Gen. Chem.2022, 92, 418-423], using ligands derived from phosphane (stripping with acid solutions) [Karamzadeh, Z.; Yaftian, M.R.; Shiri-Yekta, Z. ; Nilchi, A.; Dolatyari, L. Iran. J. Chem. Chem. Eng.2016, 35, 89-95], methylimidazoles [excellent selectivities against uranium(VI) and Ln(III)] [Li, W.; Yang, S.; Lv, H.; Liu, Z.; Wu, J.; Li, S.; Shen, Y. Radiochim. Acta2016,104,681-690], with trioctylphosphine oxide [Shiri-Yekta, Z.; Yaftian, M.R.; Nilchi, A.J. Iran. Chem. Soc.2013,10,221-227], with an aqueous solution of N,N'-dimethyl-N,N'-dioctyl-4-oxaheptanediamide (DMDOHA) [Ren, P.; Li, Y.; Wang, Z.; Geng, Y.; Yu, T.; Hua, R. Chem. Pap.2020,74,2049-2057], with carbamoylmethylphosphine oxides (CMPO) [Turanov, A. N.; Karandashev, V.K.; Yarkevich, A. N.; Khvostikov, V. A.Radiochemistry2019,61,694-699; Turanova, A. N.; Karandashevb, V. K.; Yarkevichc A. N.Radiochemistry2013,55,382-387], with polymeric CMPO [Annam, S.; Rao, C. V. S. B.; Sivaraman, N.; Sivaramakrishna, A.; Vijayakrishna, K. React. Funct. Polym.2018,131,203 210], N,N,N,N-tetraoctyl diglycolamide (TODGA) and other derivatives [Zhang, Y.; Liu, Z.; Fan, F.; Zhu, L.; Shen, Y.Sep. Sci. Technol.2014,49,1895-1902; Feng, S.; Xinghai Shen, Radiochim. Acta2020,108,757-767], tetradentate amides [Alyapyshev, M. Y.; Babain, V. A.; Tkachenko, L. I.Radiochemistry2014, 56, 565-574] and N,N-di(2-ethylhexyl)-diglycolamic acid [Ibrahim, S. M.; Zhang, Y.; Xue, Y.; Yang, S.; Ma, F.; Tian, G.Solvent Ext. Ion Exc.2020,38,417-429]. Only IL such as trioctylmethylammonium nitrate [A336][NO3] [Fu, X.; Zhang, F.; Wu, Q.; Li, Y.; Huang, Q.-G.; Yan, Z.-Y.J. Radioanal. Nuc. Chem.2021, 327:1251-1258].

[0027] However, the use of so-called task-specific ionic liquids (TSILs) combined with ionic liquids has not been as frequently used. A phosphoramidate-based TSIL has been used for the selective extraction of uranium [Xie, X.; Qin, Z.; He, Y.; Xiong, P.; Huang, Z.; Mao, Y.; Wei, H.; Zhuo, L. Sci. Rep. 2017, 7, 15735–15746]. Another TSIL consisting of an ionic liquid functionalized with 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-3-imidazolium hexafluorophosphate was employed for the general extraction of Ln(III), Th(IV), and U(VI) [Turanov, A. N.; Karandashev, V. K.; Artyushin O. I.; Sharova E. V. Solvent Extr. Ion Exc.2015, 33, 540-553.], and several TSILs similar to those described were developed for the extraction of actinides [Sengupta, A.; Mohapatra, P.K.; Iqbal, M.; Huskens, J.; Verboom, W. Sep. Pur. Tech.2013,118,264-270; Ternova, D.; Ouadi, A.; Mazan, V.; Georg, S.; Boltoeva, M.; Kalchenko, V.; Miroshnichenko, S.; Billard, I.; Gaillard, C.J. Solution Chem.2018,47,1309-1325; Paramanik, M.; Raut, D.R.; Sengupta, A.; Ghosh, S.K.; Mohapatra, P. K.RSC Adv.2016, 6, 19763-19767; Saha, A.; Tiwari, N.; Deb, S.B.; Saxena, M. K. ChemistrySelect2019, 4, 7691-7697; Maria, L.; Cruz, A.; Carretas, J. M.; Monteiro, B.; Galinha, C.; Gomes, S.S.; Araújo, M. F.; Paiva, I.; Margalo, J.; Leal, J.P.Sep. Pur. Tech.2020,237,116354].

[0028] In accordance with everything described in these backgrounds, and considering that in none of the examples is a section dedicated to the recovery of the TSIL-IL extractant system (where IL corresponds to the acronym for ionic liquid), but only to the percentage of metal recovery (stripping) at the end of the extraction process, in this intellectual property protection document the need is detected to synthesize a compound that allows the selective extraction of internal transition elements (lanthanides and actinides) with very low affinity for the metallic elements of the d and p series, and their subsequent recovery with a high yield (of at least 95%), for repeated use in subsequent extraction cycles.

[0030] DESCRIPTION OF THE INVENTION

[0032] In this memory the expression "extractant mixture" refers to the composition for use in selective extraction processes of elements from the f-block series of the periodic table (i.e., elements belonging to the lanthanide and actinide series) in samples containing these together with other metals from the s, d and p series, where said extractant mixture is formed by an ionic liquid compound TSIL with formula (5), dissolved in an ionic liquid (IL), used as a solvent, where the ionic liquid used is [CYPHOS NTf2] (6).

[0035]

[0038] The present invention relates, in a first aspect, to a TSIL molecule or compound with a chemical formula (5), as well as to a formulation of an extractant mixture that is formed by said compound (TSIL) of chemical formula (5), together with the ionic liquid CYPHOS NTf2 (6).

[0039] The present invention also relates to a process for the selective extraction of actinide and lanthanide elements with a high affinity for other s, d, and p-series metals, using the TSIL extractant mixture with chemical formula (5). That is, the present invention also relates to the ability of the aforementioned extractant mixture (5)+(6) to perform liquid-liquid extractions of f-block metals from s, d, and p-series metals, and their subsequent recovery and recycling. The s, d, and p-series metals are extracted in low or negligible amounts during the extraction process using the developed extractant mixture.

[0041] Advantageously, the extractant mixture made from the compound TSIL of chemical formula (5) and IL (6) can be recycled after the extraction and separation of the extracted elements is completed.

[0043] The synthesized TSIL compound of formula (5) is reproduced below, and not only this compound but also a chemically acceptable salt thereof is subject to protection.

[0046]

[0049] On the other hand, the extractant mixture or composition for use in selective extraction processes of metals from the two f series is also protected, such that said extractant mixture is formed from the TSIL compound of formula (5) and the ionic liquid used as a solvent [CYPHOS NTf2] (6), which is commercially available or readily prepared through simple ion exchange. In the extractant mixture, the TSIL compound of formula (5) is added in varying proportions, with a preferred concentration of 0.005 M.

[0052]

[0055] Thus, the preparation of the compound TSIL with chemical formula (5) is carried out from the antibiotic ciprofloxacin (1) using conventional functional group transformations. Specifically, the synthesis of the compound TSIL (5) takes place in three steps performed under mild conditions (i.e., using a temperature between ambient and 0°C, atmospheric air pressure, etc.) and is viable on an industrial scale.

[0057] First, the intermediate compound (2) is obtained by W-alkylation reaction of ciprofloxacin (1) with 1-bromoethane in the presence of excess W,W-diisopropyl(ethyl)amine (DIPEA), preferably in a mixture of water and acetonitrile at 40°C for 16 h.

[0060]

[0063] In the second step, Weinreb amide (4) is synthesized from an amidation reaction using excess W,0-dimethylhydroxylamine (3), preferably in the presence of thionyl chloride in dichloromethane (DCM) and triethylamine, at 0°C and for 30 minutes.

[0064]

[0067] The third step, leading to the final TSIL structure (5), consists of alkylation by adding excess 1-iodononane to the intermediate product (4) using acetonitrile as the solvent, preferably, and refluxing the mixture for two days. The resulting compound, once purified, was treated with lithium bis(trifuromethanesulfonyl)amide to generate the final product (5) by ion exchange.

[0070]

[0073] It should be noted that the main interaction of inner transition metals with TSIL(5), which acts as a selective chelating agent, occurs through the 1,3-dicarbonyl region, enhanced by the donor character provided by the Weinreb amide. This inductive effect is presumed to further strengthen the Lewis base character of the aforementioned dicarbonyl region, allowing it to have a higher affinity for the harder Lewis acids in the periodic table of elements (such as the f-block elements).

[0075] On the other hand, the present invention relates to the selective extraction process of inner transition metals, using the compound TSIL of formula (5). Advantageously, this process allows for the subsequent separation and recovery of the extractant mixture for recycling, so that the process can be adapted and implemented on a larger scale. As detailed below, the selective extraction of f-block metals from other s-, d-, and p-series metals is carried out at pH 6.

[0077] Thus, specifically, the following steps form the procedure for selectively extracting f-block metals from a sample containing f-block metals and other s, d, and p-series metals:

[0079] - Preparation of an extractant composition from the TSIL compound of formula (5) and the ionic liquid [CYPHOS NTf2] (6), wherein the TSIL compound of formula (5) is added in varying proportions, preferably at a concentration of 0.005 M.

[0080] - Introduction into a test tube of a sample to be separated containing one or more metals from the f block and other metals belonging to the s, d and p series. Adjustment of the sample to a pH of 6 by the addition of a phosphate buffer.

[0081] - Introduction into a test tube (with a volume greater than 5 ml) of the sample prepared in the previous step and addition of the extractant composition prepared in the first step, in a ratio of at least 2:1, where 1 is the extractant composition.

[0082] - Shake the test tube with the solution prepared in the previous step for at least 3 minutes.

[0083] - Resting of the solution prepared in the previous stage, differentiating two liquid-liquid phases of different densities.

[0084] - Separation of the two phases, where the organic phase corresponds to the extractant composition which includes the f series metals initially contained in the sample to be separated.

[0085] - Addition to the organic phase recovered in the previous stage of an acidified solution at pH 0.5.

[0086] - Agitation of the solution obtained in the previous stage.

[0087] - Resting of the solution prepared in the previous stage, differentiating two liquid-liquid phases of different densities.

[0088] - Separation of the two phases, where the organic phase corresponds to the extractant composition and the aqueous phase contains the metal(s) of the f-block series.

[0089] Thus, advantageously, the described procedure allows the recovery of at least 95% of the organic phase corresponding to the extractant composition containing the TSIL compound of formula (5).

[0091] BRIEF DESCRIPTION OF THE DRAWINGS

[0093] To complement the description that follows and to help in a better understanding of the characteristics of the invention, according to a preferred embodiment thereof, a set of images or figures is included as an integral part of said description, in which, for illustrative and non-limiting purposes, the following has been represented:

[0095] Figure 1 shows a schematic of the selective extraction process of the f-block metal(s) versus the s, d and p-series metals and of the procedure of a preferred embodiment of the invention.

[0097] Figure 2 shows a schematic of the procedure followed for the recovery of the f-block metal(s) from a solution used in the procedure detailed in the previous figure.

[0099] DETAILED DESCRIPTION OF THE INVENTION

[0101] As discussed above, the first step in the synthesis of the TSIL compound with formula (5) consists of the W-alkylation of ciprofloxacin (1) (commercially available) with ethyl bromide, preferably in an acetonitrile/water mixture. (Scheme 1).

[0104]

[0105] The second reaction step consisted of an amidation of Weinreb on (2) using W,O-dimethylhydroxylamine (3), after in situ generation of the corresponding acid chloride with thionyl chloride in dichloromethane and triethylamine, at 0°C for 30 minutes. This compound was preferably washed with water three times and the product (4) was recrystallized from diethyl ether (Scheme 2).

[0107]

[0110] The final step of the synthetic process involves molecule (4), which was reacted with one equivalent of 1-iodononane, preferably in refluxing acetonitrile for two days. The solvent was evaporated under vacuum, and then ion exchange was performed with lithium bis(trifluorosulfonyl)amide in dichloromethane at room temperature for 8 hours (Scheme 3). TSIL (5) was isolated with a final yield of 86%.

[0112]

[0115] Examples

[0117] Example 1: Preparation of compound (2)

[0118] A solution of 1 equivalent of ciprofloxacin hydrochloride in MeCN:H2O (30 mL/mmoL) was prepared in a flask with 6.66 equivalents of diisopropylethylamine in an ice bath under inert conditions. Five equivalents of bromoethane and 0.10 equivalents of potassium iodide were then added dropwise. The mixture was stirred for 1 hour. The flask was then placed in an oil bath at 40°C and stirred for 16 hours. Finally, the solvent was evaporated under vacuum, and the residue was dissolved in 40 mL of DCM and washed with a phosphate buffer solution at pH 6.5. The organic phase was dried with MgSO4, and the solvent was evaporated under reduced pressure to obtain compound (2) as a white solid. Yield 92%.

[0120] Example 2: Compound preparation (4)

[0121] One equivalent of compound (2) was added to a round-bottom flask along with three equivalents of triethylamine and the minimum amount of dry DCM. Then, under inert conditions and at 0°C, three equivalents of W,O-dimethylhydroxylamine (3), three equivalents of triethylamine, and 1.1 equivalents of thionyl chloride were added. The mixture was stirred for 30 minutes at this temperature. The volatile compounds were then removed under vacuum. The residue was dissolved in chloroform and washed three times with a saturated sodium bicarbonate solution to remove ammonium salts. It was then washed three times with a saturated potassium carbonate solution to remove unreacted compound (2). The organic solvent was dried with magnesium sulfate, and the solvent was evaporated under vacuum. Finally, compound (4) was obtained as a yellowish solid after recrystallization with diethyl ether. Yield 88%.

[0123] Example 3: Preparation of the compound (5)

[0124] A solution of 1 equivalent of compound (4) was prepared in a pressure tube along with 2 equivalents of 1-iodononane using the minimum possible amount of dry acetonitrile under inert conditions. The mixture was stirred under reflux for 2 days. The solvent was then removed under reduced pressure, and the residue was dissolved in chloroform. 1.3 equivalents of lithium bistriflamide (dissolved in water) was added, and the mixture was stirred overnight. The aqueous phase was then washed 3 times, the organic solvent fractions were combined, and the mixture was washed with water 3 times. The organic phase was dried with MgSO4, and the solvent was removed by rotary evaporation. Compound (5) was obtained as a white solid after recrystallization with ethyl acetate. Yield 86%.

[0126] Example 4: Selective Extraction Processes of f-Series Elements at pH 6 Given the interest in extracting elements belonging to the f-series, to perform the extraction of the analytes (metals of the f-series and d-series, for example) from an aqueous sample A, 5 mL of aqueous sample A are taken in a test tube and the pH is adjusted to pH 6 with phosphate buffer solutions. 1 mL of the extractant [0.005 M of compound (5) in (6)] (solution B) is added. The test tube is vortexed for 3 minutes and the mixture is allowed to stand. The two phases are then separated, with the inner transition metal(s) remaining in solution B and the remaining metals (see Table 1) in aqueous sample A.

[0128] Figure 1 shows the detailed scheme of the selective extraction process of inner transition metals, such as Th, U, Lu, Yb, Gd, Nd, Sm, La, Y, Ce, Eu, Sc, Pr, Tb, Dy, Ho, Er, Tm (see Table 1), versus the rest of the metals in the periodic table.

[0130] The extraction efficiency of f-block metals and the remaining metals (s, p, and d series) from the periodic table using solution B was calculated by determining the concentration of these elements in the aqueous phase (A). The content of f-block metals in the organic phase (B) was estimated by difference from the content in the aqueous phase (A). The concentration ratio (solution B/aqueous sample A) is a measure of the analyte distribution coefficient (K). Thus, a higher analyte distribution coefficient (K) indicates greater extraction efficiency.

[0132] To determine the concentration of each element, the aqueous solution (A) was analyzed by inductively coupled plasma mass spectrometry (ICP-MS). For this purpose, the most abundant and interference-free isotope of each element was selected, and its signal was recorded in the aqueous sample (A). From this signal, and using the signal obtained with standards of known concentration, the concentration of each element in the sample could be calculated.

[0134] Table 1 shows some examples of the distribution coefficient for the extractant mixture containing the TSIL compound of formula (5) at an initial concentration of 0.005 M (K) at pH 6, which were calculated according to the process detailed above. The coefficient K in Table 1 is the ratio of the metal concentration in the organic phase to the aqueous phase after extraction.

[0136] Thus, in Table 1, the distribution coefficient values obtained for the f-series metals, as well as for other metallic elements of the Periodic Table that may be found in their presence at pH = 6, can be observed.

[0137] T l 1. K rmin H = .

[0139]

[0142] As can be seen from the data collected in the table above, the distribution coefficient K calculated for the f-series metals was significantly higher than for most other metals in the periodic table. The extractant mixture containing TSIL of formula (5) and solvent 6 proved to be extremely selective.

[0144] Example 5: Release of extracted metal and recovery of mixture (5+6) [with recycling of extraction system (5)+(6)].

[0145] To recover the pure (5)+(6) mixture without any metal, a solution C (5 ml) of a solution with nitric acid at pH = 0.5 is added to solution B containing the lanthanide and actinide metals in a test tube. The test tube is shaken in a vortex for 3 minutes and the aqueous solution is separated from the organic one, recovering (5)+(6) and the aqueous phase containing the f series metals.

[0147] Figure 2 shows the detailed scheme of the mixture recovery process (5)+(6).

[0149] The recovery of pure solution B with these internal transition metals was greater than 95% and could be used in several extraction cycles. That is, this recovery allows for recycling and its use in another extraction cycle.

Claims (10)

1. CLAIMS 1. The compound TSIL with chemical formula (5) 2. A composition for use in selective extraction processes of internal transition elements, wherein said composition comprises a compound according to claim 1a, characterized in that it comprises the compound TSIL of formula (5) and an ionic liquid CYPHOS NTf2(6). 3. A composition for use in selective extraction processes of internal transition elements, according to claim 2a, characterized in that the TSIL compound with formula (5) is added at a concentration of 0.005 M. 4. A method for preparing the TSIL compound with formula (5), according to claim E, characterized in that it comprises the following steps: W-alkylation reaction of ciprofloxacin (1) with 1-bromoethane in the presence of DIPEA, to generate (2), Amidation reaction with W,0-dimethylhydroxylamine (3) using thionyl chloride, obtaining the intermediate (4). Alkylation of (4) with 1-iodononane and subsequent ion exchange with lithium bis(trifurosulfonyl)amide to obtain compound (5). 5. Process for preparing the compound TSIL with chemical formula (5), according to claim 4a, characterized in that the reaction of ciprofloxacin (1) with 1-bromoethane by means of a δ-alkylation reaction is carried out in the presence of water:acetonitrile at 40 °C for 16 hours to obtain the product (2). 6. Process for preparing the compound TSIL with chemical formula (5), according to claim 4a, characterized in that the reaction of (2) and (3) with thionyl chloride is carried out in the presence of triethylamine and dichloromethane as solvent and at 0 °C for 30 minutes, generating the intermediate (4). 7. Process for preparing the compound TSIL with chemical formula (5), according to claim 4a, characterized in that the alkylation reaction of the intermediate (4) with 1-iodononane is carried out in the presence of acetonitrile and takes place under reflux for 48 hours, and then the subsequent ion exchange is carried out to give the compound (5). 8. A selective extraction process for internal transition elements in a sample, using the TSIL compound of formula (5) according to claim E, characterized in that it comprises the following steps: - Preparation of an extractant composition from the compound TSIL of formula (5) and the ionic liquid [CYPHOS NTf2] (6). - Introduction into a test tube of the sample to be separated which contains the metals of the f series and other metals belonging to the s, d and p series. - Adjusting the sample to a pH of 6 by adding a phosphate buffer. - Introduction into a test tube of the sample prepared in the previous step and addition of the extractant composition prepared in the first step in a ratio of at least 2:1, where 1 is the extractant composition. - Shake the test tube with the solution prepared in the previous step for at least 3 minutes. - Resting of the solution prepared in the previous stage, differentiating two liquid-liquid phases of different densities. - Separation of the two phases, where the organic phase corresponds to the extractant composition that includes the f series metals initially contained in the sample to be separated. - Addition to the organic phase recovered in the previous stage of an acidified solution at pH 0.5. - Agitation of the solution obtained in the previous stage. - Resting of the solution prepared in the previous stage, differentiating two liquid-liquid phases of different densities. - Separation of the two phases, where the organic phase corresponds to the extractant composition and the aqueous phase corresponds to the f series metals. Where at least 95% of the organic phase is recovered, which corresponds to the extractant composition containing the TSIL compound of formula (5). 9. A selective extraction process for internal transition elements in a sample, according to claim 8a, characterized in that in the step of preparing the extractant composition from the TSIL compound of formula (5) and the ionic liquid [CYPHOS NTf2] (6), the TSIL compound is used at a concentration of 0.005 M. 10. A selective extraction procedure for inner transition elements in a sample, according to claim 8a, characterized in that the sample to be separated contains metals of the s, p and d series, contained in the periodic table.