Katsuhiro Suenobu

Direct arylation polycondensation for the synthesis of bithiophene-based alternating copolymers

Direct arylation polycondensation reactions using a simple catalytic system gave eight kinds of bithiophene-based alternating copolymers. The conditions for the reactions of 3,3′,4,4′-tetramethylbithiophene with dibromoarylenes were optimized to obtain high-molecular-weight polymers without formation of cross-linked structures. In the reaction of a dibromoarylene containing a reactive C–H bond, a short reaction time (1.5 h) was suitable for preventing side reactions. In contrast, a long reaction time (6 h) gave high-molecular-weight polymers from dibromoarylene monomers without a reactive C–H bond. This polycondensation reaction enables the synthesis of polymers containing dye structures such as diketopyrrolopyrrole and isoindigo, which are applicable as materials for polymer solar cells.

The Catalysis of Vapor-Phase Beckmann Rearrangement for the Production of ε-Caprolactam

Recently, Sumitomo Chemical Co., Ltd. developed the vapor-phase Beckmann rearrangement process for the production of ε-caprolactam. In the process, cyclohexanone oxime is rearranged into ε-caprolactam using a zeolite as a catalyst instead of sulfuric acid. EniChem in Italy developed the ammoximation process that involves the direct production of cyclohexanone oxime without producing any ammonium sulfate. Sumitomo Chemical Co., Ltd. has commercialized the combined process of vapor-phase Beckmann rearrangement and ammoximation in 2003.In this paper, the authors focus on some aspects of the vapor-phase Beckmann rearrangement catalysis. A solid catalyst that is mainly composed of a high-silica MFI zeolite (Silicalite-1) has been developed for the vapor-phase Beckmann rearrangement. This catalyst does not possess acidity that can be detected by ammonia TPD. Methanol fed into the reactor with cyclohexanone oxime improves the yield of caprolactam. Methanol reacts with terminal silanols on the zeolite surface and converts them to methoxyl groups. The modification of the catalyst by methanol has an important role for the Beckmann rearrangement reaction.Nest silanols located just inside the pore mouth of the MFI zeolite are supposed to be the active sites of the catalyst. We propose that the coordination between the NOH group of cyclohexanone oxime molecule and the nest silanols through hydrogen bonding is responsible for the reaction. The reaction mechanism of Beckmann rearrangement under vapor-phase conditions is the same as in the liquid phase, namely, the alkyl group in anti-position against the hydroxyl group of the oxime migrates to the nitrogen atoms position.