Condensation of 2,3-dichloromaleic anhydride and o-phenylenediamine in refluxing toluene affords the three compounds 2,3-dichloro-N-o-C6H4(NH2)maleimide (1), N,N¢-o-C6H4-bis(2,3-dichloromaleimide) (2), and 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one (3), with compound 1 as the major product. Repeating the same reaction in the presence of added PTSA furnishes compound 3 as the major product. Treatment of 3 with methylthiol in the presence of pyridine affords monosulfide compounds 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one (4) and and the disulfide derivatives 2,3-di(methylthio)pyrrolo[1,2-a]benzimidazol-1-one (5). The substitution of the first chlorine group in compound 3 occurs regioselectively at C-3 to produce compound 4, followed by replacement of the remaining chlorine group to furnish the disulfide compounds 5. The new compounds 1-5 have been isolated by column chromatography and characterized by IR, NMR, XRD, CV and etc.

Novel cage-functionalized azacrown ethers, i.e. 51, 52, 53, 55, 57, 61 and 62, which have various crown cavity and different number of nitrogen atoms incorporated, have been prepared. X-ray structures of 53, 55 and 57 have been obtained for the study of the crown topological structure. The complexation properties of crown 51, 52, 57, 61 and 62 have been evaluated via alkali metal picrate extraction, silver picrate extraction and ESI-MS study. The novel cage-fuctionalized azacrown ethers generally exhibit high avidity and selectivity towards Ag+ versus alkali metal ions and some transition metals i.e. Cu2+, Mn2+, Zn2+, Ni2+ and Pb2+. Crown 61 displays significant avidity and selectivity toward K+ in alkali metal picrate extraction experiments vis-à-vis the remaining alkali metal picrates. Three types of ditopic ion-exchange receptors for sodium hydroxide extraction study have been designed. All of the crown ether molecules have proper cavity for selective sodium complexation and have weakly acidic ionizable alcohols for sodium-proton exchange under strongly basic conditions. Crown 80 and 81 were synthesized; key intermediates for the synthesis of crown 82, 83 and 84 have been prepared. The preparation of 99 afforded an unexpected crown 103. The preparation of 109 had been attempted, but could not be …