Green Synthesis Of Macrocyclic Supramolecular Sulfonylthiourea-based Receptors And Their Molecule Recognition Of Anions

The synthetic method of macrocyclic supramolecular sulfonyl thiourea receptors was developed, based on the research progress of the synthetic method of thiourea derivatives, the utilization of macrocyclic receptors and of sulfonamide-mediated reactions as nucleophilic reagent. Twenty-six new key intermediates and seven ty-eight undocumented topic compounds were synthesized conveniently. Complex action of these macrocyclic receptors with anions containing amino acid and Lewis acid was roughly explored. Including three parts are as follows:Tetraethylene glycol ditosylates, N,N’,N’’-tri-tosyl-diethylenetriamine and N-tosyl aziridines were synthesized in the presence of inorganic base NaOH or KOH in aqueous media. p-tert-butyl-calix[4]arene was synthesized taking HCHO and NaOH as meterial. Detertbutyl, hydroxybenzene （crown） etherification, aromatic nitration, aromatic amination and aromatic chlorosulfonylation, aminosulfonylation and ipso-chlorosulfonylation were performed on the platform of calixarene. Such intermediates as calix[4]arene, p-tert-butyl-calix[6]arene and methoxyethoxy- etherification calix[4]arene, N,N’-dimethylcarbonylmethy-etherification calix[4]arene, 1,3-diaminocalix[4]arene and p-tert-butyl-calix[4]-bis（crown-5） and 1,3-alternative diaminocalix[4]-crown-5 were designed and synthesized according to the improved procedures of literature.Calix[4]-crown-5-sulfonyl tetrahydroimidazo thione-2 and hexahydropyrimidine thione-2 were synthesized from calix[4]-crown-5-sulfonylethylenediamine and carbon disulfide through nucleophilic addition and subsequent cyclization of intramolecule promoted by ClCH₂COOK at room temperature in aqueous solution. In this paper, as a part of our program towards green synthesis, a series of calix[6] -sulfonyl tetrahydroimidazo thione-2 and hexahydropyrimidine thione-2 and N-calix[4]arene-N’-aryl or alkylsulfonyl-thioureas and N-calix[4]arenesulfonyl- N’-aryl or alkyl-thioureas were also synthesized. Their desulfonylation products were obtained in the presence of Mg and MeOH, subsequent oxidation products were given promoted by H₂O₂ through grinding. Macrocyclic cyclophane-based thiourea derivatives were synthesized that the nucleophilic reaction of diamines and carbon disulfide in aqueous NaOH afforded a series of bis-dithiocarbamate salts. Activation of these with aqueous ClCH₂COOK and subsequent nucleophilic substitution reaction with trisulfonamide aqueous KOH at room temperature provided N-tosyl-macrocycles containing two thiourea units, whose desulfonylation and subsequent oxidation were also carried out. This strategy has the advantages of simple operation, mild reaction condition, easy product-isolation and environmental friendliness.A series of anions such as H₂PO₄^-, HSO₄^-, C1-, NO₃^-, ClO₄^- was studied , which was found that calix[4]-bissulfonylthiourea receptor 78a showed higher selective complexation capability with H₂PO₄^- . The binding properties of calix[4]-tetrasulfonylthiourea receptor 81c with anions such as F^-, CH3COO^-, Cl^-, Br^-, I^-, NO₃^- were examined by UV-Vis and 1H NMR spectroscopy methods. The results showed that the receptor 81c had a better selectivity to Cl-over other anions. The extraction experiments for amino acids showed that compound 92b exhibited good selective extraction ability for isoleucine. From the IR and 1H NMR of complex [M（62）]Cl₂ , it was well concluded that macrocyclic receptor 62 had a better binding action with MCl₂ than reference compound. From the 1H NMR spectra, one pair of doublets for the ArCH2Ar protons can be split as 1:1, as a result, a flattened cone structure was kept after inclusion.