This report focuses on epoxy‐dicyandiamide (DICY) curing system accelerated by N‐aryl‐N′,N′‐dialkyl urea, aiming at clarifying the accelerating mechanism and the relationship between accelerating effect and molecular structure of the accelerators. Nine N‐aryl‐N′,N′‐dialkyl ureas were synthesized and investigated with measurements of differential scanning calorimetry, thermo gravimetric/differential thermal analysis and NMR spectroscopy. The results revealed that the ureas released the corresponding secondary amines by the thermal dissociation in the presence of epoxide, which led to the formation of tertiary amines that catalyze the addition reaction of DICY to epoxide. Moreover, a tendency that the ureas able to release more compact amines exhibited higher acceleration effects was discovered. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

[reaction: see text] An enantiospecific synthesis of a coccinellied alkaloid, (-)-adalinine, was established starting from (S)-(-)-pyroglutamic acid, where a stereoselective Michael addition and a samarium iodide-promoted regioselective carbon-nitrogen bond cleavage reaction were involved as the key reactions.

A new class of thermally latent initiators for the ring‐opening polymerization of epoxides has been developed. The latent initiators developed herein were the hydroxylamides 1a, 1b, and 1c, which were synthesized from phthalide, 3‐isochromanone, and cis‐cyclohexahydrophthalide, respectively, by their ring‐opening reactions with pyrrolidine. These hydroxylamides were designed so that their hydroxyl groups could attack the amide moiety intramolecularly upon heating, leading to ring closure and formation of the corresponding lactones while releasing pyrrolidine, the initiator for the anionic ring‐opening polymerization of an epoxide. The temperatures at which this thermal dissociation occurred were strongly dependent on the hydroxylamide molecular structure. When using the hydroxylamides as thermally latent initiators, the polymerizations of bisphenol‐A diglycidyl ether were investigated at various temperatures. This investigation clarified that the threshold temperature, that is, the temperature at which polymerization was initiated, increased in the order of 1a, 1b, and then 1c. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2611–2617

The meso and racemic forms of 1,3‐bis(hydroxyphenylmethyl)benzene underwent solvent‐free polycondensation with the aid of an acid catalyst giving polyether. Very interestingly, the diastereoisomerism caused a considerable difference in the polymerization behavior. The meso isomer (mp = 96–98 °C) was polymerized even at 65 °C, whereas the racemic one (mp = 158–160 °C) required heating at 100 °C to undergo polymerization. However, the latter produced a much higher molecular weight than the former (30,000 vs 4000). The contamination of the meso isomer with the racemic one very sensitively reduced the polymerization temperature: the 98.5% meso monomer underwent polymerization at 50 °C. In contrast to solvent‐free polymerization, two diastereomeric monomers showed almost identical behavior in solution polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3564–3571, 2003