Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical “vinyl” polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105–125 °C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds). A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (φ in %). In particular, the high φ values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion “vinyl” polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.

1. This study provides the first evidence that stilbene oxide and styrene oxide are reductively metabolized to the corresponding alkenes by intestinal bacteria in animals. 2. When trans- or cis-stilbene oxide were incubated with the caecal contents of rat under anaerobic conditions, both trans- and cis-stilbene were isolated from the incubation mixture. Styrene oxide was also reduced to styrene by rat caecal contents. 3. Caecal contents of mouse, hamster and guinea pig also exhibited alkene oxide reductase activities toward cis- and trans-stilbene oxides, and styrene oxide. In contrast, liver microsomes or cytosol exhibited no epoxide reductase activities toward these substrates. 4. Seven pure strains of intestinal bacteria exhibited alkene oxide reductase activities of varying degrees under anaerobic conditions, with the highest activity being observed in Clostridium sporogenes. 5. Cell-free extracts of either the intestinal bacteria in rat caecal contents or C. sporogenes exhibited reductase activity when supplemented with both NAD(P)H and FMN under anaerobic conditions. Reductase activity was also observed on addition of the photochemically reduced form of FMN instead of both NAD(P)H and FMN.

Our previous study reported that operation in multiple steady states contributes to an improvement in reaction conversion, making it possible to reduce the energy consumption of the reactive distillation process for tert-amyl methyl ether (TAME) synthesis. This study clarified the factors responsible for an improvement in the reaction conversion for operation in the multiple steady states of the reactive distillation column used in TAME synthesis. The column profiles for those conditions, in which multiple steady states existed and those in which they did not exist, were compared. The vapor and liquid flow rates with the multiple steady states were larger than those when the multiple steady states did not exist. The effect of the duty of the intermediate condenser, which was introduced at the top of the reactive section, on the liquid flow rate for a reflux ratio of 1 was examined. The amount of TAME production increased from 55.2 to 72.1 kmol/h when the intermediate condenser was operated at 0 to −5 MW. Furthermore, the effect of the intermediate reboiler duty on the reaction performance was evaluated. The results revealed that the liquid and vapor flow rates influenced the reaction and separation performances, respectively.