成果報告書詳細
管理番号20110000000681
タイトル*平成22年度中間年報 グリーン・サステイナブルケミカルプロセス基盤技術開発 有害な化学物質を削減できる、又は使わない革新的プロセス及び化学品の開発 高機能不均一触媒の開発と環境調和型化学プロセスの研究開発(H21~H23)
公開日2011/7/28
報告書年度2010 - 2010
委託先名大学共同利用機関法人自然科学研究機構分子科学研究所
プロジェクト番号P09010
部署名環境部
和文要約和文要約等以下本編抜粋:1.研究開発の内容及び成果等 (1)有害な化学物質を削減できる、又は使わない革新的プロセス及び化学品の開発 a「錯体触媒を利用した水中不均一条件での精密化学合成法の開発研究」 本項目については、現在最も汎用性が高く、また有効な炭素骨格形成法として知られる、芳香族ハライドと芳香族ボロン酸とのカップリングによる炭素~炭素結合形成工程(Suzuki-Miyaura 反応)および芳香族ハライドとアミンとのカップリングによる炭素~窒素結合形成反応(Buchwald-Hartwig 反応)を標的反応として選択した。
英文要約This GSC research project performed by Uozumi’s team comprises 3 major subjects: (1) Green Coupling Catalysis with Transition Metal Complexes, (2) Green Aerobic Oxidation of Alcohols with Nano-Metal Catalyst, (3) Efficient Catalytic Protocol for Esters and Amides Preparation. (1) Green Coupling Catalysis with Transition Metal Complexes: Previously, we have reported that carbon-carbon and carbon-nitrogen bond forming reactions (the so-called Suzuki-Miyaura coupling and Buchwald-Hartwig reaction, respectively) were catalytically achieved in water with polymer-immobilized palladium complexes with a high level of chemical greenness. In particular, a catalytic carbon-nitrogen bond forming reaction of aryl halides and various amines in water with a polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported di(t-butyl)phosphine-palladium complex catalyst was applied to a clean process for preparing TPD derivatives, hole-transporting agents for EL-devices, via the aromatic amination of 4,4’-dibromobiphenyl with diarylamines without any metal contamination. However, the chemical yield of TPDs, cost of the polymer support, and co-production of halogen-based chemical waste still remain as major problems to be solved. In the FY2010, we developed a chitosan-protected gold nano catalyst which found to catalyze the homo-coupling of a variety of arylboronic acids in water under aerobic conditions to afford the corresponding biaryl compounds. It is also noteworthy that chitosan is a biomass-based material to meet the green chemical requirement. With the novel homo-coupling catalysis in hand, we started to investigate the formation of TPDs via the homo-coupling of 4-(diarylamino)phenylboronic acid. This process is under thorough condition screening. (2) Green Aerobic Oxidation of Alcohols with Nano-Metal Catalyst: We have already reported that PS-PEG resin-dispersion of platinum nano particles, which were developed in Uozumi’s group, were found to promote aerobic oxidation of various primary and secondary alcohols in water under heterogeneous conditions to give the corresponding carbonyl compounds. This aerobic oxidation was applied to prepare alkyl(oligo (ethylene glycol))carboxylic acids which have been recognized as potential anionic surfactants for extra-fine electronic devices. In FY2010, a novel flow liquid-gas reactor, X-Cube was installed in Uozumi’s laboratory which made thorough screening of pressure, temperature, and catalyst-contact time conditions possible in a combinatorial manner. The aqueous aerobic oxidation of 1-phenylethanol was found to be completed within 37.5 sec of the catalyst-contact time (flow-rate = 0.8 mL/min) at 100 °C under 50 bar of oxygen gas pressure. The aerobic oxidation of alkyl(oligo (ethylene glycol)) was achieved in water using a cartridge of PS-PEG resin-supported Pt nano catalyst under a 60 bar pressure of oxygen gas at 100 °C for 50 sec of the catalyst-contact time (0.6 mL of aqueous starting alcohol solution/min) without any additives to give the targeted alkyl(oligo (ethylene glycol))carboxylic acids in a quantitative yield where any contaminated metal species was not detected by ICP-AES analysis. The flow oxidation was continued for almost 26 hours where 16 grams of the targeted acid was obtained and TON reached at 249. Pilot production of alkyl(oligo (ethylene glycol))carboxylic acids provided 20-40 grams of the acids which are subjected to the experiment in the washing process of fine electronic devices. (3) Efficient Catalytic Protocol for Esters and Amides Preparation: This subject has been studied at Nagoya University as a trust-study subject. Prof. Ishihara at Nagoya University has l\already developed a novel catalytic system for the dehydrative formation of imides etc. by use of aryl boronic acid derivatives having bulky 2,6-substituents as catalysts in FY2009. In FY2010, Ishihara developed a catalytic trans esterification protocol with a lanthanide salt.
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