5411-14-3Relevant academic research and scientific papers
(Trifluoromethylselenyl)methylchalcogenyl as Emerging Fluorinated Groups: Synthesis under Photoredox Catalysis and Determination of the Lipophilicity
Grollier, Kevin,De Zordo-Banliat, Arnaud,Bourdreux, Flavien,Pegot, Bruce,Dagousset, Guillaume,Magnier, Emmanuel,Billard, Thierry
supporting information, p. 6028 - 6033 (2021/03/15)
The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two-step strategy based on a metal-free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88 %, which raised to 98 % in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physicochemical characterization of these emerging groups was performed by determining their Hansch–Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95 %. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives.
Synthesis and Evaluation of Bifunctional [2.2.2]-Cryptands for Nuclear Medicine Applications
McDonagh, Anthony W.,McNeil, Brooke L.,Patrick, Brian O.,Ramogida, Caterina F.
supporting information, p. 10030 - 10037 (2021/07/19)
For the first time, synthesis of bifunctional [2.2.2]-cryptands (CRYPT) and demonstration of radiolabeling with lead(II) (Pb2+) isotopes are disclosed herein. The synthesis is convenient and high-yielding and gives access to three distinct bifunctional handles (azide (-N3), isothiocyanate (-NCS), and tetrazine (-Tz)) that can enable the construction of radioimmunoconjugates for targeted and pretargeted therapy. Proof-of-principle CRYPT radiolabeling was successful with lead-203 ([203Pb]Pb2+) and demonstrated complexation efficiency superior to that of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) and efficiency comparable to that of the current industry standard TCMC (1,4,7,10-tetraaza-1,4,7,10-tetra-(2-carbamoylmethyl)-cyclododecane). In vitro human serum stability assays demonstrated excellent [203Pb]Pb-CRYPT stability over 72 h (91.7 ± 0.56%; n = 3). [203Pb]Pb-CRYPT-radioimmunoconjugates were synthesized from the corresponding CRYPT-immunoconjugate or by conjugating [203Pb]Pb-Tz-CRYPT to transcyclooctene modified trastuzumab (TCO-trastuzumab) via the inverse electron-demand Diels-Alder (IEEDA) reaction. This investigation reveals the potential for CRYPT ligands to become new industry standards for therapeutic and diagnostic radiometals in radiopharmaceutical elaboration.
Impregnated copper ferrite on mesoporous graphitic carbon nitride: An efficient and reusable catalyst for promoting ligand-free click synthesis of diverse 1,2,3-triazoles and tetrazoles
Khalili, Dariush,Rezaee, Meysam
, (2019/09/17)
Magnetic CuFe2O4/g-C3N4 hybrids were synthesized through a facile method and their catalytic performances were evaluated in click chemistry for the first time. The structural and morphological characterization of prepared materials was carried out by different techniques such as X-ray diffraction, high-resolution transmission electron microscopy, field emission scanning electron microscopy, Fourier infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, and N2 adsorption–desorption analysis (Brunauer–Emmett–Teller surface area). The utilization of magnetic CuFe2O4/g-C3N4 enabled superior performance in the one-pot azide–alkyne cycloaddition reaction in water using alkyl halides and epoxides as azide precursors without the need of any additional agents. The present system is broad in scope and especially practical for the synthesis of macrocyclic triazoles and also tetrazoles. In addition, the catalytic system highly fulfills the demands of “green click chemistry” with its convenient conditions, especially easy access to a variety of significant products in low catalyst loading and simple work-up and isolation procedure.
Triazole-amide isosteric pyridine-based supramolecular gelators in metal ion and biothiol sensing with excellent performance in adsorption of heavy metal ions and picric acid from water
Panja, Atanu,Ghosh, Kumaresh
, p. 934 - 945 (2019/01/09)
Pyridine-based small molecular gelators 1-4, having a triazole-amide isosteric relationship, have been synthesized. Compounds 1-3 exhibit excellent gelation from DMSO-H2O (1?:?2, v/v), while compound 4 forms a gel in the presence of Ag+ ions in DMSO-H2O (1?:?2, v/v). The change from triazole to isosteric amide has a marked effect on the gelling abilities, minimum gelation concentrations (mgc), thermal stability, mechanical properties, metal ion-responsive character and adsorption properties of the structures, as established by various techniques. All the gels have been successfully applied in sophisticated sensing kits for the selective detection of Cu2+ and Ag+ ions and thiol-containing amino acids. The triazole-based gelators 1 and 3 adsorb heavy metal ions from water with greater efficiency than the isosteric amide-based gelators. The metallogel 4-Ag+ can be used in the efficient removal of picric acid (a nitro explosive) from water.
Iron(III) Metallacryptand and Metallacryptate Assemblies Derived from Aroylbis(N,N-diethylthioureas)
Pham, Chien Thang,Nguyen, Hung Huy,Hagenbach, Adelheid,Abram, Ulrich
, p. 11406 - 11416 (2017/09/25)
The reaction of isophthaloylbis(N,N-diethylthiourea), H2L1, with FeCl3·6H2O gives the dinuclear tris-complex [Fe2(L1)3] (5), possessing a cryptand-like structure. A similar reaction with the ligand 2,6-dipicolinoylbis(N,N-diethylthiourea), H2L2, however, results in the formation of the anionic, mononuclear Fe(III) complex [Fe(L2)2]- (6), which could be isolated as its "Tl+ salt" by the subsequent addition of Tl(NO3). A tighter view to the solid state structure of the obtained product, however, characterizes compound 6 as a one-dimensional coordination polymer, in which four-coordinate Tl+ ions connect the {[Fe(L2)2]-} units to infinite chains. When Fe3+ ions and Tl+ ions are added to H2L2 simultaneously in a one-pot reaction, a different product is obtained: a cationic trinuclear complex of the composition {M?[Fe2(L2)3]}+. It has been isolated as a PF6- salt and represents a {2}-metallacryptate with a nine-coordinate Tl+ ion in the central void. Structurally related products of the compositions {M?[Fe2(L2)3]}(PF6) (M = Na+, K+, Rb+) (8(PF6)) could be isolated from analogous reactions with alkaline salts instead of Tl(NO3). {2}-Metallacryptates with larger central voids were synthesized with the ether-spaced aroylbis(N,N-diethylthiourea) H2L3. The compounds {M?[Fe2(L3)3]}(PF6) (M = K+, Rb+, Tl+ or Cs+) (9(PF6)) were prepared by a similar protocol like those with H2L2 with the simultaneous addition of the metal ions to a solution of H2L3. Due to the larger spacer between the aroylthiourea units, the coordination number of the central M+ ions is 12 by six carbonyl and six ether oxygen atoms. All products were characterized by elemental analysis, IR spectroscopy, and X-ray structure analysis. Cyclic voltammetric studies were carried out with the three representative complexes [Fe2(L1)3], {K?[Fe2(L2)3]}(PF6), and {K?[Fe2(L3)3]}(PF6). The obtained voltammograms indicate the dependence of the redox properties of the oligonuclear systems on the conjugation in the organic backbones of the ligands.
Snapshotting the excited-state planarization of chemically locked N,N′-disubstituted dihydrodibenzo[a,c]phenazines
Chen, Wei,Chen, Chi-Lin,Zhang, Zhiyun,Chen, Yi-An,Chao, Wei-Chih,Su, Jianhua,Tian, He,Chou, Pi-Tai
supporting information, p. 1636 - 1644 (2017/02/10)
For deeper understanding of the coupling of electronic processes with conformational motions, we exploit a tailored strategy to harness the excited-state planarization of N,N′-disubstituted dihydrodibenzo[a,c]phenazines by halting the structural evolution via a macrocyclization process. In this new approach, 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) is used as a prototype, in which the para sites of 9,14-diphenyl are systematically enclosed by a dialkoxybenzene-alkyl-ester or-ether linkage with different chain lengths, imposing various degrees of constraint to impede the structural deformation. Accordingly, a series of DPAC-n (n = 1-8) derivatives were synthesized, in which n correlates with the alkyl length, such that the strength of the spatial constraint decreases as n increases. The structures of DPAC-1, DPAC-3, DPAC-4, and DPAC-8 were identified by the X-ray crystal analysis. As a result, despite nearly identical absorption spectra (onset ～400 nm) for DPAC-1-8, drastic chain-length dependent emission is observed, spanning from blue (n = 1, 2, ～400 nm) and blue-green (n = 3-5, 500-550 nm) to green-orange (n = 6) and red (n = 7, 8, ～610 nm) in various regular solvents. Comprehensive spectroscopic and dynamic studies, together with a computational approach, rationalized the associated excited-state structure responding to emission origin. Severing the linkage for DPAC-5 via lipase treatment releases the structural freedom and hence results in drastic changes of emission from blue-green (490 nm) to red (625 nm), showing the brightening prospect of these chemically locked DPAC-n in both fundamental studies and applications.
Synthesis of new lariat ethers containing polycyclic phenols and heterocyclic aromatic compound on graphite surface via mannich reaction
Sharghi,Khalifeh,Salimi Beni
experimental part, p. 275 - 288 (2010/11/05)
Synthesis of novel lariat ethers containing polycyclic phenols and heterocyclic aromatic compound using graphite via Mannich reaction are herein described. For this purpose N-(methoxymethyl) azacrown ether 4 was synthesized in nearly quantitative yield. The reaction of N-(methoxymethyl) azacrown ether 4 with polycyclic phenols and heterocyclic aromatic compound was performed in 10-20 min in the presence of graphite. The graphite powder can be reused up to five times after simple washing with acetone.
Efficient synthesis of some novel macrocyclic diamides using fast addition method
Sharghi, Hashem,Zare, Abdolkarim
, p. 999 - 1004 (2007/10/03)
Synthesis of some new macrocyclic diamides based on catechol scaffold by cyclization reactions between various diamines and 2-[2-(2-chloro-2-oxoethoxy) phenoxy]ethanoyl chloride using fast addition method has been described. The reactions were carried out in short reaction times and the expected macrocycles were obtained in good to high yields. Georg Thieme Verlag Stuttgart.
Synthesis, characterization and ion transportation studies of some novel cyclophane amides
Rajakumar, Perumal,Rasheed, A. Mohammed Abdul
, p. 5351 - 5362 (2007/10/03)
Various novel cyclophane amides with a large cavity have been synthesized. The structures of cyclophane amides 14 and 15 were resolved using XRD studies. Cyclophane amide 28 shows a shift in λmax in the UV/Vis. spectra when treated with Cu (II) ion as well as with Pb (II) ion. Ion transportation studies were carried out with cyclophane amide 14 which proved that the Na+ ion passes through the cavity while K+ ions are retained.
Synthesis of 1,1,1-trichloro-2,2-bis-(carboxymethoxyaryl)ethanes as potential antimicrobial and insecticidal agents
Purohit,Shah
, p. 618 - 622 (2007/10/03)
Some new 1,1,1-trichloro-2,2-bis-(carboxymethoxyaryl)-ethanes 2a-t have been synthesised by the treating aryloxyacetic acid (two moles) with chloral hydrate (1 mole) in the presence of catalytic amount of conc. sulphuric acid. The aryloxyacetic acid are prepared by the reaction of substituted phenols with chloroacetic acid in the presence of aq. sodium hydroxide. The antimicrobial activity of these compounds have been assayed against various Gram+ve, Gram-ve bacteria and fungi. The constitution of the products have been elucidated by IR, 1H NMR and mass spectral data and elemental analyses.
