Marichev K. Synthesis and properties of new types of carbenoids of azole series. Macrocyclic and polymeric systems

New macrocyclic 3-oxapentylene, 3,6-dioxaoctylene, tetra-, hexa- and dodecamethylene bridged bisimidazolium and bisbenzimidazolium salts were synthesized via the quarternization of the corresponding bisazoles by dihalogenalkanes. Respective 1,1',3,3'-bis(3-oxa-1,5-pentylene)bis-2Н-benzimidazoline, crown-bisazolthiones and bisazolselenones were obtained by the carbenoid reactions of crown-bisazolium salts with sodium borohydride, sulfur and selenium, and crown-bisazolones by the reaction of crown-bisazolselenones with epichlorhydrin. New crown-biscarbene and polycarbene complexes of transition metals (copper, silver, nickel, palladium) were obtained under the deprotonation of crown-bisazolium and polymeric azolium salts by sodium hydride or potassium tert-butoxide in organic solvents in the presence of metal compounds. A stable macrocyclic poly-1,1',3,3'-bis(3-oxa-1,5-pentylene)bisbenzimidazol-2-ylidene was synthesized for the first time from the corresponding crown-bisazolium salt under the action of potassium tert-butoxide. The carbenoid transformations of the polymer proceeded with organic electrophiles (methyliodide, phenylisothiocyanate, N-phenylmaleimide) to form macrocyclic 2-substituted azolium salts, zwitterionic compounds, bisazolines. The high catalytic efficiency of carbenes was found in transesterification of ethylbenzoate into methylbenzoate (TON and TOF are obtained to be significantly higher than the data indicated in the literature). The high antimicrobial activity of 1,1',3,3'-bis(1,12-dodecamethylene)bisimidazolium salts was found in vitro: chloride - for S. aureus (МBSC 31.2 and МBCC 62.5 mg/l), M. luteum (МBSC and МBCC 3.9 mg/l); thiocyanate - for S. aureus (МBSC 3.9 and МBCC 7.8 mg/l), M. luteum (МBSC 1.9 and МBCC 3.9 mg/l).