23978-10-1Relevant articles and documents
Steric and stereoelectronic effects in aza crown ether complexes
Solov'ev, Vitally P.,Strakhova, Nadezhda N.,Kazachenko, Vladimir P.,Solotnov, Alexandr F.,Baulin, Vladimir E.,Raevsky, Oleg A.,Ruediger, Volker,Eblinger, Frank,Schneider, Hans-Joerg
, p. 1379 - 1389 (1998)
Stability constants and enthalpy changes determined by calorimetric titrations and supported by selected NMR titrations are reported for the complexation of sodium and potassium cations with 18 different crown ethers containing nitrogen atoms with different number, location and substitution pattern. The data, measured in methanol mostly with potassium salts, are compared to literature data; they show striking differences between all-oxygen analogs and the macrocycles with NH groups. In contrast, affinities with aza crown ethers bearing alkyl groups at the nitrogen as well as with the cryptand [2.2.2] come closer to the complexation free energies predicted from the number and electron donating capacity of the ligand heteroatoms. This is rationalised on the basis of molecular mechanics calculations, showing that a NH-containing crown predominates in conformations with axial N lone pairs, due to their repulsive electrostatic interactions with the ring oxygen atoms. Replacement of the hydrogen by alkyl groups forces the lone pairs to an equatorial position, thus enabling better complex formation, as borne out by experiment. In line with these arguments the IgK differences are with some exceptions more due to ΔH than to TΔS differences. The calorimetric data show linear isoequilibrium correlations between TΔS and ΔH, with slopes between those observed with other crown ether and cryptand complexes. Preliminary investigations of some synthetic macrocyclic amide precursors yield appreciable complexation only, if the two carbonyl oxygens can come in close contact with the guest cation. Computer aided molecular modelling shows that this is possible in a small 15C5-derivative, in which the polyethylenglycol cycle only serves as ring template without binding contributions from the ether oxygen atoms.
MACROHETEROCYCES. XXXVI. A CONVENIENT METHOD FOR SYNTHESIS OF DI- AND POLYAZACROWN ETHERS
Luk'yanenko, N.G.,Basok, S.S.,Filonova, L.K.
, p. 1562 - 1571 (2007/10/02)
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.
Chemistry of crown ethers XIX. Functionalized crown ethers for the solubilization of barium sulfate
Jong, F. de,Zon, A. van,Reinhoudt, D. N.,Torny, G. J.,Tomassen, H. P. M.
, p. 164 - 173 (2007/10/02)
The use of seawater as injection fluid in oil-producing formations often leads to blocking of the wells as a result of barium sulfate-scale formation.Macrocylic complexants specifically designed to solubilize barium sulfate efficiently into water have been synthesized and their BaSO4-solubilizing capacities have been determined.The stability of barium complexes of macrocyclic polyethers can be greatly increased by the introduction of flexible side-chains containing anionic groups.Most of newly synthesized complexants, based mainly on diaza-18-crown-6, give very stable complexes.However, many o f them are extremely insoluble in water.Only bis(carboxymethyl)diaza-18-crown-6, bis(phosphonomethyl)diaza-18-crown-6 and, to a lesser extent, bis(dicarboxymethyl)diaza-18-crown-6 and bisdiaza-18-crown-6 are efficient solubilizers of BaSO4 in water.