ZnCl2/PhI=O Mediated Selective ortho-Chlorination of Amides

: A new ortho-chlorination system consisted of zinc(II) and hypervalent iodine(III) reagent was developed for ortho-chlorination of amides, and the desired products were obtained in moderate to good yields (38 - 85%). This highly facile and convenient methodology was tolerant of aromatic amide and alkyl amide with diverse substituted groups. A plausible mechanism was illustrated in which carbocation rearrangement and metal salt coordinate facilitated ortho-chlorination were involved.

Segmented-Block Poly(ether amide)s Containing Flexible Polydisperse Polyethyleneoxide Sequences and Rigid Aromatic Amide Moieties

We describe the synthesis and characterization of three novel aromatic diamines containing oxyethylene sequences of different lengths. These diamines were polymerized using the low-temperature solution polycondensation method with isophthaloyl chloride (IPC), terepthaloyl chloride (TPC), [1,1’-biphenyl]-4,4’-dicarbonyl dichloride (BDC), and 4,4′-oxybis(benzoyl chloride) (OBE), obtaining twelve poly(ether amide)s with short segments of polydisperse polyethyleneoxide (PEO) sequences in the polymer backbone. These polymers show reasonably high molecular mass materials (Mw > 12,000), and the relationship between their structure and properties has been carefully studied. Compared with conventional polyamides containing monodisperse PEO sequences, the polydispersity of the PEO segments within the structural units exerts a significant influence on the crystallinity, flexibility, solubility, and the thermal properties of the polymers. For instance, the all-para oriented polyamides (TPCP-A), with an average number of 8.2 ethylenoxide units per structural unit can be transformed conventionally (Tm = 259 °C) in comparison with thermally untransformable polymer with 2 ethylenoxide units (Tm = 425 °C).