Branched cationic polyurethane prepared by polyaddition of chloromethylated five‐membered cyclic carbonate and diethylenetriamine in molten salts

A branched cationic polymer was synthesized by polyaddition of 4‐chloromethyl‐1,3‐dioxolan‐2‐one and diethylenetriamine in molten salts. The polyaddition proceeded through nucleophilic addition of the primary amino group to the cyclic carbonate structure and quarternization of the secondary amino group with the chloromethyl group. The resulting cationic polymer was a good and recyclable catalyst for the reaction of carbon dioxide and epoxides owing to the ammonium structure. The complexation with DNA was confirmed by dynamic light scattering and zeta potential measurements, and it suggests the potential application as a carrier for drug delivery system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dispersion polymerization accompanied by CO2 fixation: Synthesis of particles of polymers bearing cyclic carbonate and epoxide moieties

Radical dispersion polymerization of glycidyl methacrylate accompanied by CO₂ fixation yielded particles of polymers bearing cyclic carbonate and epoxide moieties in the presence of polymeric dispersion stabilizers. Cellulose acetate successfully stabilized the dispersion, whereas poly(N‐vinylpyrrolidone) did not. Spherical particles with diameters of 1–10 μm could be prepared under the optimized conditions. The epoxide moieties in the particle were hydrolyzed selectively keeping the shapes of the particles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Reactivity of Hydroxy‐ and Aquo(hydroxy)‐λ3‐iodane–Crown Ether Complexes

We have designed a series of hydroxy(aryl)‐λ³‐iodane–[18]crown‐6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown‐6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non‐hygroscopic shelf‐storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions. Furthermore, hydroxy‐λ³‐iodane–[18]crown‐6 complexes serve as efficient progenitors for the synthesis of diaryl‐, vinyl‐, and alkynyl‐λ³‐iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases.     

Synthesis, structure, and reaction of 1-alkynyl(aryl)-lambda3-bromanes

Reported here for the first time are the synthesis, structure, and reaction of hypervalent 1-alkynyl(aryl)-lambda3-bromanes. BF3-catalyzed ligand exchange on bromine(III) of p-trifluoromethylphenyl(difluoro)-lambda3-bromane with 1-alkynyl(trimethyl)stannanes in dichloromethane at -78 degrees C afforded 1-alkynyl(aryl)-lambda3-bromanes in good yields. Trimethyl(trimethylsilylethynyl)stannane gave silylethynyl-lambda3-bromane selectively. 13C NMR chemical shifts of acetylenic carbon atoms of alkynylbromanes are compared with those of alkynyl-lambda3-iodanes and explained in terms of the spin-orbit-induced heavy atom effects. The structure of tert-butylethynylbromane was established by a single-crystal X-ray analysis of its crown ether complex. The 1-alkynyl(aryl)-lambda3-bromanes serve as highly electron-deficient Michael acceptors and undergo tandem Michael-carbene rearrangements by the reaction with sulfonate anions, yielding 1-alkynyl sulfonates.