Macroheterocycles; LVII.¹Improved Synthesis of Azacrown Ethers with Phenolic Sidearms

New phenol-containing bis(azacrown ether)s: synthesis and complexing properties

“…The preparation of ortho-aminomethylated phenols 5 , 6 with free para-positions is typical of many described examples of the Mannich reaction. l o Evidently, a six-member transition state forms, a in most cases of aminomethylation of phenols.…”

“…Probably, hydrogen bonding between the OH group and groups in the ortho-position of the last mentioned phenols prevents the aminomethyl substituents from being introduced because p-hydroxybenzaldehyde and p-nitrophenol give substitution products l c and Id in good yields. 6 We failed to introduce two monoazacrown ether substituents on to one phenolic ring by aminomethylation of parasubstituted phenols in benzene at 80 "C. However, symmetric bis(azacrown ether)s 14a+ were prepared using refluxing xylene as the solvent (Scheme 2). Aminomethylation also allowed the preparation of asymmetric binuclear ligands by a two-step reaction of the appropriate phenol at 80 "C and then at 144 "C. The interaction of equivalent amounts of p-cresol with N-methoxymethyl-substituted azacrowns in CCl, at 80 "C gave monoaminomethylation products 17,lS.…”

“…Heavy oil (75%); 6 was refluxed with the appropriate para-substituted phenol (2 mmol) for 12 h under nitrogen. After removing the xylene at reduced pressure from the mixture, the final products were purified by column chromatography on neutral aluminium oxide using chloroform-benzene (1 : 1 v/v) and then chloroformbenzene (2 : 1 v/v).…”

Synthesis of new lariat ethers containing polycyclic phenols and heterocyclic aromatic compound on graphite surface via mannich reaction

“…Condensation of the N-(methoxymethyl) azacrown ether 4 and Į-naphtol with appropriate solvent was carried out under reflux conditions (entries 1, 3, 5) [11,12]. The final product 5 was obtained in 2 h of heating with low yields (10-19%).…”

Synthesis, Characterization, Antibacterial,Antifungal and Anticancer Studies of a New Antimetabolite: N-[(Diphenylamino)methyl]acetamide and Some of Its Inner Transition Metal Chelates

“…With their versatile structures, redox behavior and physicochemical properties, inner transition metal complexes are often useful as chemical nucleases 1 . The interaction of these complexes with DNA has gained much attention due to their possible applications as new therapeutic agents.…”