陸川 政弘

Background: Developing environmentally benign processes, such as organic reactionsconducted in water, is desired from the view of sustainable technology. Concerning the palladiumcatalyzedborylation reactions of aryl halides in water, only a few examples have been reported. Objective: This study aimed to develop efficient methods for palladium-catalyzed borylation reactionsof aryl halides in water, not only increasing product yields but also extracting products withless organic solvents. Methods: We adopted polymer surfactants, such as diblock copolymers that consist of poly(Nisopropoylacrylamide)and a hydrophilic segment, and a poly(ethylene glycol)-based polymer thatconsists of poly(ethylene glycol) chain and 4-chloromethylbenzyl moiety. Results: Reactions using these polymers gave the borylation products in significantly higher yieldsthan that in pure water. The efficiency of the extraction process for the products from the reactionmixtures was evaluated, indicating that the polymer micelles enabled separation processes with lessorganic solvent. Conclusion: Applying polymer surfactants increased the product yields in Pd-catalyzed borylationof aryl halides, and it enabled the extraction of the products from the aqueous reaction mixture moreefficiently.

Pd complexes covalently tethered on thermoresponsive polymer catalysed coupling reactions in water.

Abstract: Ruthenium-catalyzed olefin metathesis reactions were conducted in water with thermoresponsiveblock copolymers forming micelles. The block copolymers were prepared by living radicalpolymerization and consisted of a thermo-responsive and hydrophilic segments. The formersegment included poly(N-isopropylacrylamide) or poly(N,N-diethylacrylamide), and the latterpoly(sodium 4-styrene sulfonate), poly(sodium 2-acrylamido-2-methylpropanesulfonate) orpoly(ethylene glycol). Homometathesis, cross-metathesis and ring-closing metathesis reactions proceededto afford the products in moderate to good yields. Extraction efficiency from the reactionmixture was also studied.

S-6X multi-block copolymers can be developed by direct one-pot copolymerization via Ni(0) coupling reaction, allowing high conductivity and strength on a wide-range of IECs.

A few kinds of thermoresponsive diblock copolymers have been synthesized and utilized for palladium-catalyzed coupling reactions in water. Poly(N-isopropylacrylamide) (PNIPAAm) and poly(N,N-diethylacrylamide) (PDEAAm) are employed for thermoresponsive segments and poly(sodium 4-styrenesulfonate) (PSSNa) and poly(sodium 2-acrylamido-methylpropanesulfonate) (PAMPSNa) are employed for hydrophilic segments. Palladium-catalyzed Mizoroki–Heck reactions are performed in water and the efficiency of the extraction process is studied. More efficient extraction was observed for the PDEAAm copolymers when compared with the PNIPAAm copolymers and conventional surfactants. In the study of the Sonogashira coupling reactions in water, aggregative precipitation of the products was observed. Washing the precipitate with water gave the product with satisfactory purity with a good yield.

Cellulose is the main component of biomass and is the most abundant biopolymer on earth; it is a non-toxic, low-cost material that is biocompatible and biodegradable. Cellulose gels are receiving increasing attention as medical products, e.g., as wound dressings. However, the preparation of cellulose hydrogels employing unmodified cellulose is scarcely reported because of the cumbersome dissolution of cellulose. In previous studies, we developed the new promising cellulose solvent N-butyl-N-methylpyrrolidinium hydroxide in an aqueous solution, which can dissolve up to 20 wt% cellulose within a short time at room temperature. In this study, we employed this solvent system and investigated the gelation behavior of cellulose after crosslinker addition. The swelling behavior in water (swelling ratio, water uptake), the mechanical properties under compression, and the antibacterial activity against Escherichia coli and Bacillus subtilis were investigated. We have developed a simple and fast one-pot method for the preparation of cellulose gels, in which aqueous pyrrolidinium hydroxide solution was acting as the solvent and as an antibacterial reagent. The pyrrolidinium hydroxide content of the gels was controlled by adjustment of the water volume employed for swelling. Simple recovery of the solvent system was also possible, which makes this preparation method environmentally benign.

<p>Poly(<italic>p</italic>-phenylene)-based sulfonated polymers with well-controlled IECs were synthesized <italic>via</italic> a three-step procedure including preceding sulfonation of precursor monomers.</p>