- Polyazamacrocyclic compounds for complexation of metal ions
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The present invention relates to a new polyazamacrocyclic compound or a salt thereof and its uses. The compound has the formula STR1 where x is 2, 3 or a combination of p 2(s) and q 3(s) where p+q=y; y is 3 or 4; R is (CH2)z P(=0)R1 R2 ; R1 is R3 or OR3 where R3 is alkyl, cycloalkyl or aryl; R2 is H, alkyl or STR2 where R4 is alkyl, cycloalkyl or aryl; and z is 1 to 3. In one important embodiment, this compound may be complexed with a metal to be a polyazamacrocyclic compound-metal complex having the formula STR3 where r is 2 or 3; and Me is a metal ion.
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- Triflamides for protection and cyclization of tetraamines to tetraazamacrocycles
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A facile two-step synthesis of tetraazamacrocycles is reported starting from trifluoromethanesulfonyl derivatives of linear tetraamines. After cyclization, the macrocycle was deprotected using sodium in liquid ammonia.
- Panetta,Yaouanc,Handel
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p. 5505 - 5508
(2007/10/02)
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- MACROHETEROCYCLES. 15.* SYNTHESIS OF MACROCYCLIC POLYAMINES IN A BIPHASIC SYSTEM
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Macrocyclic polyamines are conveniently synthesized by condensation of bissulfonamides with ditosylates or dibromides of glycols in the biphasic system toluene(xylene)-aqueous sodium hydroxide.
- Luk'yanenko, N. G.,Basok, S. S.,Filonova, L. K.,Kulikov, N. V.,Pastushok, V. N.
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p. 346 - 349
(2007/10/02)
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- MACROHETEROCYCLES. PART 44. FACILE SYNTHESIS OF AZACROWN ETHERS AND CRYPTANDS IN A TWO-PHASE SYSTEM
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A facile procedure is proposed for the preparation of azacrown ethers and cryptands by condensation of dibromides or ethylene glycol bis(toluene-p-sulphonate)s with acyclic bis(sulphonamide)s or with bisdiazacrown ethers, respectively.The reaction was carried out in a two-phase system of aqueous alkali-toluene (benzene)in the presence of quaternary ammonium salts as phase transfer catalysts.The catalytic activity decreased in the sequence: Bu4NI ca.Bu4NBr > Bu4NCl > Bu4NHSO4 > Et3NCH2C6H5NCl.Maximum yields of twelve-membered azacrown ethers are obtained when lithium hydroxide is used, while crown ethers of larger size are observed in the presence of sodium or potassium hydroxides; this may be due to a template effect.
- Lukyanenko, Nikolai G.,Basok, Stepan S.,Filonova, Lyubov K.
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p. 3141 - 3148
(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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- σ-Bonded organochromiuin(III) complexes. 3. Decomposition in acid solution of chromium(III) complexes containing pyridylmethyl and polydentate amine ligands
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The decomposition of σ-bonded (pyridylmethyl)chromium complexes, 2- and 3-NC5H4CH2CrLn (L = dap (1,3-diaminopropane), dien (diethylenetriamine), trien (triethylenetetramine), and [15]aneN4 (tetraazacyclopentadecane)), was investigated in aqueous perchloric acid under aerobic conditions. Except for L = 15[ane]N4, Cr-C bond scission was preceded by complete aquation in the case of the 2-isomers and partial aquation for the 3-isomers. The aquation rates were compared with those of inorganic chromium complexes containing similar amine ligands. Kinetic data for the Cr-C bond cleavage were correlated with those for the analogous ethylenediamine (en) and aquo (H2O) systems. The activation parameters and product studies are in support of a homolytic pathway for the Cr-C bond cleavage.
- Crouse, Karen,Goh, Lai-Yoong
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p. 478 - 484
(2008/10/08)
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- A microcalorimetric determination of the enthalpies of formation in solution of nickel(II) complexes with tetraaza macrocyclic ligands of varying size
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The enthalpies of formation of nickel complexes with tetraaza macrocyclic ligands of varying ring size, from 12 to 15 members, have been determined by destroying the complexes in aqueous solution with alkaline cyanide. The octahedral-square-planar equilibria have been investigated, and the results are presented as ΔH° for both octahedral, blue and, when possible, square-planar, yellow species. Like the Cu(II) system, the blue, octahedral series exhibits a maximum in ΔH° with [14]aneN4. This is discussed in terms of the relative size of the ligand and the metal ion. The unexpected reversal of ΔH° for the two square-planar complexes is rationalized in terms of expected ligand transformations.
- Fabbrizzi, Luigi,Micheloni, Mauro,Paoletti, Piero
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p. 535 - 538
(2008/10/08)
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