Polymer-bound crown ethers were obtained by Mannich reaction of benzocrown ethers with amino polymers, polycondensation of dibenzo-18-crown-6 with acyl dichlorides, and polycondensation of benzocrown ethers with formaldehyde and aromatic compounds. Complexation reactions with potassium thiocyanate or picrate as well as with perchloric acid were used for crown ether group determination. The reaction kinetics of polymer-bound crown ethers with potassium iodide were studied.
Synthetic applications of polymer-bound purine and pyrimidine derivatives, based on their tautomerism, have been studied. The chloropyrimidine derivatives, which were highly reactive and could revert to the more stable lactam form, were particularly useful for dehydration and dehydrosulfanylation reactions. Alkoxypyrimidines were thermally cleaved to give olefins or esters, causing lactim to lactam transformation. Dissociation of alkylthio groups from thioalkylpurines and thioalkylpyrimidines took place under basic conditions to give olefins, indicating another example of tautomeric transformation.
Conditions for preparing polymer-supported metal complex catalysts by polymerization and copolymerization of metal-containing monomers (MCM), i.e., compounds with a metal-containing unit and a multiple bond capable of polymerization, were analysed. Three main types of MCM, their composition and structure, and peculiarities of their homo- and copolymerization are described. The main conversions different from polymerization of conventional monomers are highlighted. The structural arrangement of both the metal complexes and the MCM-based polymers are considered, as well as the conversion observed upon incorporation in the macrochain. The main directions of application of MCM and MCM-based polymers in catalysis are defined.
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