- Superalkali-Alkalide Interactions and Ion Pairing in Low-Polarity Solvents
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The nature of anionic alkali metals in solution is traditionally thought to be "gaslike"and unperturbed. In contrast to this noninteracting picture, we present experimental and computational data herein that support ion pairing in alkalide solutions. Concentration dependent ionic conductivity, dielectric spectroscopy, and neutron scattering results are consistent with the presence of superalkali-alkalide ion pairs in solution, whose stability and properties have been further investigated by DFT calculations. Our temperature dependent alkali metal NMR measurements reveal that the dynamics of the alkalide species is both reversible and thermally activated suggesting a complicated exchange process for the ion paired species. The results of this study go beyond a picture of alkalides being a "gaslike"anion in solution and highlight the significance of the interaction of the alkalide with its complex countercation (superalkali).
- Riedel, René,Seel, Andrew G.,Malko, Daniel,Miller, Daniel P.,Sperling, Brendan T.,Choi, Heungjae,Headen, Thomas F.,Zurek, Eva,Porch, Adrian,Kucernak, Anthony,Pyper, Nicholas C.,Edwards, Peter P.,Barrett, Anthony G. M.
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supporting information
p. 3934 - 3943
(2021/04/06)
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- High-efficiency environment-friendly low-cost synthetic method of cycleanine
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The invention discloses a high-efficiency environment-friendly low-cost synthetic method of cycleanine. The synthetic method comprises the following steps: step a, mixing triethylene tetramine, water,potassium carbonate and acetone to obtain a mixture, separately adding paratoluensulfonyl chloride into the mixture in different batches, and synthesizing a compound 2; step b, adding the compound 2and 1,2-dibromoethane into a solvent, and synthesizing a compound 3 in the presence of alkaline metal carbonate; step c, adding water and sulfuric acid into the compound 3, adding ethanol into a reaction product, precipitating, discharging, centrifuging, collecting a solid product, adding water and active carbon into the solid product, stirring, decoloring, centrifuging, collecting filtrate, adding hydrochloric acid, perfor ming salting-out crystallization, precipitating, discharging, centrifuging, collecting the solid product, and obtaining a compound 4; and step d, taking the compound 4 andan alkaline substance as raw materials, synthesizing a cycleanine crude product, extracting and purifying by virtue of methylbenzene-water, and obtaining the cycleanine. The high-efficiency environment-friendly low-cost synthetic method has the advantages of low cost, high efficiency, environmental friendliness.
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Paragraph 0034; 0035; 0036
(2018/04/28)
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- Synthesis of an azacrown template for phosphatidylinositol-4,5-bis(phosphate) recognition
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An azacrown system has been developed for selective membrane binding of phosphatidylinositol-4,5-bis(phosphate) recognition. Neutral and cationic forms of the metacyclophane macrocycles have been synthesized by divergent routes in acceptable yields. Such
- Gray Jr., Charles W.,Barry, Kathleen,Lindberg, Eric J.,Houston, Todd A.
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p. 2683 - 2686
(2008/02/03)
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- Preparation and animal biodistribution of 166Ho labeled DOTA for possible use in intravascular radiation therapy (IVRT)
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Owing to its favorable decay characteristics (T1/2 = 27 h, Eβ(max) = 1.85 MeV, Eγ = 81 keV) and its availability with a specific activity of 3.74.4GBq/mg from a moderate flux reactor, 166Ho can be considered as a potential radionuclide for intravascular radiation therapy (IVRT) using liquid-filled balloons. In the present work, studies on the use of 166Ho labeled 1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) as a possible agent for IVRT for the prevention of restenosis has been initiated. 166Ho was obtained by irradiating natural Ho2O3 powder and DOTA was synthesized by a multistep procedure. The optimum protocol of radiolabeling of DOTA with 166Ho was achieved by varying different reaction parameters. The complex was found to retain its stability for 7 days at room temperature. Bioevaluation studies carried out in Wistar rats showed that >95% of the injected activity was excreted within 3 h p.i. with almost no retention in any major organ. Both radiochemical and biological studies showed that 166Ho labeled DOTA can be further explored as a potential agent for IVRT. Copyright
- Das, Tapas,Chakraborty, Sudipta,Banerjeel, Sharmila,Samuel, Grace,Sarma,Venkatesh, Meera,Pillai
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p. 197 - 209
(2007/10/03)
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- Preparation of hexaaza and heptaaza macrocycles functionalized with a single aminoalkyl pendant arm
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A practical and reproducible route for the preparation of 1,4,7,10,13,16,19-heptaazacyclohenicosane (1), 1,4,7,10,13,16-hexaazacyclooctadecane (2), and 1,4,7,10,13,17-hexaazacycloicosane (3) bearing a single N-(2-amino-ethyl) pendant arm has been develope
- Zhang, Zhibo,Mikkola, Satu,Loennberg, Harri
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p. 854 - 858
(2007/10/03)
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- Manganese complexes of nitrogen-containing macrocyclic ligands effective as catalysts for dismutating superoxide
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The present invention is directed to low molecular weight mimics of superoxide dismutase (SOD) represented by the formula: STR1 wherein R, R', R1, R'1, R2, R'2, R3, R'3, R4, R'4, R5, R'5, R6, R'6, R7, R'7, R8, R'8, R9, and R'9 and X, Y, Z and n are as defined herein, useful as therapeutic agents for inflammatory disease states and disorders, ischemic/reperfusion injury, stroke, atherosclerosis, hypertension and all other conditions of oxidant-induced tissue damage or injury.
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- Methods of preparing manganese complexes of nitrogen-containing macrocyclic ligands
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The present invention is directed to low molecular weight mimics of superoxide dismutase (SOD) represented by the formula: STR1 wherein R, R', R1, R'1, R2, R'2, R3, R'3, R4, R'4, R5, R'5, R6, R'6, R7, R'7, R8, R'8, R9, and R'9 and X, Y, Z and n are as defined herein, useful as therapeutic agents for inflammatory disease states and disorders, ischemic/reperfusion injury, stroke, atherosclerosis, hypertension and all other conditions of oxidant-induced tissue damage or injury.
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- 1,4,7,10,13,16,19,22-Octaazacyclotetracosane-l,4,7,10,13,16,19,22- octaacetic acid (H8OTEC) and 1,4,7,10,14,17,20,23-octaazacyclohexacosane-1,4,7,10,14,17,20,23-octaacetic acid (H8OHEC): Synthesis and characterization of two large macrocyclic p
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The optimized synthesis of two new macrocyclic polyamine polycarboxylic ligands, 1,4,7,10,14,17,20,23-octaazacyclohexacosane-1,4,7,10,14,17,20,23-octaaceticacid (H8OHEC) (10) 1 and 1,4,7,10,13,16,19122-octaazacyclotetracosane-1,4,7,10, 13,16,19
- Schumann, Herbert,Boettger, Ulrike A.,Zietzke, Kerstin,Hemling, Holger,Kociok-Koehn, Gabriele,Pickardt, Joachim,Ekkehardt Hahn,Zschunke, Adolf,Schiefner, Birgit,Gries, Heinz,Raduechel, Bernd,Platzek, Johannes
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p. 267 - 277
(2007/10/03)
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- Synthesis and characterization of various unsubstituted and mono-N-substituted tetraazamacrocycles
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Syntheses of tetraazamacrocycles have been carried out by using p-toluenesulfonyl chloride as protective group.The and were also obtained by the template synthesis.Mono-N-functionalization of tetraazamacrocycles was accomplished by reaction of a fivefold excess of the free macrocycles with 1 equivalent of a suitable alkylating or arylating reagent.The key point of the synthesis lies in the use of an excess of the macrocycle over the substituting reactants to reduce the formation of polysubstituted derivatives, and in the easy separation of the excess of unreacted macrocycle.All the products were characterized on the basis of spectral studies (1H and 13C NMR, including 2D NMR and NOE difference studies) and mass spectrometry.Key words: tetraazamacrocycles, improved synthesis, protective group, N-tosylation, template synthesis, NOE difference spectroscopy.
- Meunier, I.,Mishra, A. K.,Hanquet, B.,Cocolios, P.,Guilard, R.
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p. 685 - 695
(2007/10/02)
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- MACROHETEROCYCES. XXXVI. A CONVENIENT METHOD FOR SYNTHESIS OF DI- AND POLYAZACROWN ETHERS
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A method is proposed for the production of di- and polyazacrown ethers by the condensation of bissulfonamides with dibromides or ditosyloxy derivatives in a two-phase aqueous alkali-toluene (benzene) system.The optimum concentration range for the substrate and the alkylating agent is 0.017-0.1 M.The catalytic activity of the quaternary ammonium salts decreases in the order (Bu)4NI > (Bu4)NBr > (Bu4)NCl > (Bu4)NHSO4 > (C2H5)3C6H5CH2NCl >> (Et)4NI > (Et)4NBr.The highest yields of te 12-membered azacrown ethers are obtained in the presence of lithium hyroxide, and the largest yields of the crown ethers with larger ring sizes are obtained in the presence of sodium or potassium hydroxide, and this is probably due to the matrix effects of the cation.
- Luk'yanenko, N.G.,Basok, S.S.,Filonova, L.K.
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p. 1562 - 1571
(2007/10/02)
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- Synthesis and Characterization of Macrocyclic Polyaza(2,5)pyridinophanes Possessing Vitamin B6 Functionality
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Series of macrocyclic polyaza(2,5)pyridinophanes (poly = tri, tetra, penta; m = 9, 12, 15) (8-10) and polyazaparacyclophanes (11-13) were synthesized in excellent yields by the reaction of dichloropyridoxine derivatives (4) and α,α'-dibromo-p-xylene (5), respectively, with a series of 1,2-ethanediamine derivatives (1-3).These phanes were characterized on the basis of 1H NMR spectra.The methyl group at C6 of the pyridoxine moiety (a-series) revealed restricted rotation for all bridge sizes (m = 9-15).In 8-10 without the methyl group (b-series), m = 12 was the boundary between restricted and free rotation.In series 11-13, only 11 (m = 9) showed restricted rotation.Atomic group equivalence was discussed terms of boundary restricted rotation and an empirical rule for the prediction of the relationship between the bridge size and restricted rotation was proposed.
- Iwata, Masaaki,Kuzuhara, Hiroyoshi
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p. 1031 - 1036
(2007/10/02)
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- Bifunctionalization of α,ω-Sulphonamides via Kinetically Controlled Reaction of α,ω-Bis(N-nitrososulphonamides)
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α,ω-Bis(N-nitrososulphonamides) in hot benzene were converted into α,ω-disulphonates and bifunctional α-sulphonate-ω-sulphonamides, in good yields, by intramolecular N-nitrososulphonamide-sulphonate rearrangement.
- Iwata, Masaaki,Kuzuhara, Hiroyoshi
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p. 918 - 919
(2007/10/02)
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- SYNTHESE DE COORDINATS MACROCYCLIQUES POLYAZOTES COMPORTANT UNE FONCTION AMINE SECONDAIRE DISCRIMINEE
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A synthetic scheme is elaborated to prepare two polyaza-macrocycles in which one nitrogen atom is distinct from the others.Thus, (tri-N-methyl)-1,4,7,10-tetraazacyclododecane and (tetra-N-methyl)-1,4,7,10,13-pentaazacyclopentadecane were synthesised.Throu
- Pilichowski, J. F.,Lehn, J. M.,Sauvage, J. P.,Gramain, J. C.
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p. 1959 - 1964
(2007/10/02)
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- Synthesis of macrocyclic polyamines: Application to the increase of urinary excretion of copper in rats
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The properties of six chelating agents that form highly stable complexes with transition metals has been examined in a comparative study for the elimination of copper in rats. For cyclic ligands, effectiveness grows with the stability constants of their complexes with this metal. With respect to Trien L5 and Penicillamine L6, aliphalic ligands used in human therapy the 1,4,7,10,13-pentaazacyclopentadecane has proven to be more effective. After treatment by this macrocyclic polyamine, urinary excretion reached 60 times that observed in the control animals. The acute toxicity measurements in mice demonstrated that the intrinsically slightly toxic ligands are less so than their corresponding complexes. Considered in their entirety these results, with L2, permit the inference of an improvement in Wilson's disease therapy.
- Pilichowski,Borel,Meyniel
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p. 425 - 431
(2007/10/02)
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- Co-ordinating Tendencies of a 14-Membered Tetra-aza Macrocycle which forms a Seven-membered Chelate Ring
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The basicity constant of 1,4,7,10-tetra-azacyclotetradecane (L5) and the stability constants of the complexes 5>(2+) and 5)>(3+) have been determined by potentiometry at 25 deg C in 0.5 mol dm-3 K
- Micheloni, Mauro,Paoletti, Piero,Poggi, Antonio,Fabbrizzi, Luigi
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- 12-Alkyl-1,4,7,10-tetraazacyclotridecane
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12-alkyl-1,4,7,10-tetraazacyclotridecane of the formula STR1 wherein R is an alkyl group containing at least 8 carbon atoms. This compound can be used for capturing metal ions.
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- Asymmetric macrocycles containing oxygen and binaphthyl ring members
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Chiral, hinged and functionalized host multiheteromacrocycles of the oxygen, nitrogen and sulfur-containing type are disclosed possessing holes sized to afford selective complexation of specific guest substances and shapes to recognize chirally guest molecules by virtue of the chiral steric barrier of the 2,2'-diheteroatom-1,1'-binaphthyl grouping, the naphthyl-naphthyl dihedral angle, and the provision of ortho positioned side chain substituents (arms) bearing terminal functional groups which act as counterions or additional complexing sites, and the provision of remote position side chain substituents used to control solubility and volatility properties or to bond the multiheteromacrocycles to solid supports.
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