巻号一覧
61 巻, 5 号
選択された号の論文の16件中1～16を表示しています
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御園生 誠2003 年 61 巻 5 号 p. 406-412
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe basic concept of green chemistry as well as the two reasons why it is necessary (the realization of the limit of massive growth and the necessity of risk management of chemicals) and three aims are described. The aims are substantial reduction of environmental impact, the improvement of economical efficiency and performance, and the establsihment of good realtionhsip between chemistry and society. For the sound development of green chemsitry, the evaluation of overall greenness of product or process is indispensable. It has been pointed out that, as for green organic syntheses, the efficiencies of reaction itself and the following separation and purification steps are critical.抄録全体を表示PDF形式でダウンロード (1150K) -
河本 光明2003 年 61 巻 5 号 p. 413-418
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーGreen sustainable chemistry (GSC) program promotes the research, development, and implementation of innovative chemical technologies that accomplish pollution prevention and chemical risk reduction. Supporting and promoting the research and development of innovative green sustainable chemical technologies is the main part of GSC program. Also, it is important for Japanese industry to develop new businesses using the output of GSC research & development.抄録全体を表示PDF形式でダウンロード (1137K) -
安井 至2003 年 61 巻 5 号 p. 419-424
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリー環境負荷による影響を定量的に表現することは,実はそれほど簡単なことではない.しかし,今後,社会をより持続可能型へと変革するためには,このような方法論が確立する必要がある.これに対し,科学的には不可能なのではないか,それを目指すζとは無駄なのではないか,と誤解されることがある.実は,このような方法論を科学的に確立することが必要であると主張している訳ではない.厳密な意味で科学的に確立するには,地球上のすべての対象物についてすべての知識を得る必要がある.すなわち,環境負荷の影響を定量的に表現することは,自然科学のすべてに近い意味合いを持ってしまい,明らかに不可能である.ここで確立する必要があると主張するのは,「その妥当性について,社会的な合意が得られること」を意味している.
歴史的に見れば,これまでの環境対策は,ヒトや生態系に対するリスクをゼロに近づけることを目標として実行されており,実際にかなりうまく機能してきた.ところが,現時点のように,かなりのリスクが回避され,リスクが突出しているというものが見当たらない状況になると,「初めから少ないリスクをさらにどこまで少なくすべきか」という観点からの議論が必要であると同時に,「そのリスクの減少の過程で,何か別のリスクの発生は心配ないのか」,といった発想,すなわち,トータルにみてリスクの総計が減少するようなポリシーを採用する必要がある.これが環境負荷の影響を総合的に評価するということの中身であるが,上述のように,厳密にこれを行うことは不可能である.もともと突出したリスクがない状況であるのならば,どのリスクを下げるかは,むしろ,社会的合意に基づいて行うことが,住民サービスとしても,また,社会的な安定性を高める意味からも妥当であるように思える.
すなわち,環境負荷の影響評価には,個人の感覚,主観を盛り込むことが可能なシステムが必要であり,筆者の提案している時間消費法は,このような考え方に基づいて開発され,今後も改良を続けていく予定である.
化学分野におけるグリーンインデックスについても同様であり,その方法論を厳密に定めることは不可能である.そこで,多くの人々によって合意されるような方法論を探し出す知恵と,一・旦決まったことを順次改善するというポジティブかつプラクティカルな態度がもっとも求められているのである.
平成15年には,GSC賞の第二回目の表彰が行われる.しかも,繰り返しになるが,GSC賞が,大臣賞に格上げになった.その期待に答えるためには,グリーン評価の尺度が,世界的なスタンダードとなることを目指すべきだろう.抄録全体を表示PDF形式でダウンロード (992K) -
村橋 俊一2003 年 61 巻 5 号 p. 425-435
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe discovery of a new chemical reaction often leads to new chemical principle and application. We found that low valent ruthenium, rhodium, iridium, and rhenium hydride complexes can be used as transition metal-based redox Lewis acid and base, and ambiphilic catalysts. Various substrates bearing α-hetero atom (pronucleophiles) such as nitriles, carbonyl compounds, isocyanates undergo α-C-H activation upon treatment with the transition-metal-based catalysts, and subsequent reaction with nucleophiles such as alkenes, alkynes, carbonyl compounds, imines, and nitriles give the products via carbon-carbon bond formations. Nitriles undergo reactions with either nucleophiles or electrophiles under neutral conditions in the presence of transition-metalbased redox Lewis acid catalysts. The catalysts can be used also as ambiphilic catalysts. With these catalysts multi-step reactions are carried out in one pot under neutral conditions, and are highly useful for combinatorial chemistry and the reactions in microreactor. The novel transition metal complex catalyzed reactions thus obtained would give various non-salt alternative processes for industry. The concept would provide an important way for green chemistry.抄録全体を表示PDF形式でダウンロード (1608K) -
金田 清臣2003 年 61 巻 5 号 p. 436-444
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe organic reactions mediated by solid surface come closest to an ideal simplified version of chemical processes. This article describes development of heterogeneous metal catalysts aiming at 'green' carbon-carbon bond-forming reactions, based on unique properties of inorganic crystals, i.e. hydroxyapatite, montmorillonite, and hydrotalcite.
A coordinatively-unsaturated Ru species generated on the hydroxyapatite surface efficiently catalyzes Diels-Alder reaction as well as aldol reaction of nitriles with carbonyl compounds in water solvent as a Lewis acid. A robust Pd2+ species on a Ca-deficient hydroxyapatite is capable of promoting Heck and Suzuki coupling reactions.
A Sc (H2O) 6 species within the expansible interlayer space of montmorillonite shows an outstanding catalysis for Michael reaction of 1, 3-dicarbonyls even under solventless conditions. Allylation of carbonyl compounds with allyltrimethylsilane proceeds smoothly using Mn+-montmorillonite catalysts to afford homoallylic alcohols. Self-organized hydrotalcite provides a unique base catalyst in aldol reaction of aldehydes in water.
The above functionalized and recyclable solid catalysts offer 'green' protocols of carbon-carbon bond-forming reactions to replace conventional methods using stoichiometric reagents and homogeneous metal complex catalysts.抄録全体を表示PDF形式でダウンロード (1498K) -
濱田 知明, 眞鍋 敬, 小林 修2003 年 61 巻 5 号 p. 445-453
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーCatalytic asymmetric aldol reactions in aqueous media have been developed using Pr (OTf) 3 and chiral bis-pyridino-18-crown-6 1. In the asymmetric aldol reaction using rare earth metal triflates (RE (OTF) 3) and 1, slight changes in ionic diameters of the metal cations greatly affected the diastereo- and enantioselectivities of the products. It was found that the binding ability of the crown ether with the RE cation and the catalytic activity of the complex were important for achieving high selectivity in the asymmetric aldol reactions. In this reaction, water plays an essential role for the good yield and selectivities. Several aldehydes and silyl enol ethers derived from ketones and thioesters can be employed in the catalytic asymmetric aldol reactions using, Pr (OTf) 3 and 1 to provide the desired aldol adducts in good to high yields and stereoselectivities.抄録全体を表示PDF形式でダウンロード (1698K) -
鳥澤 保廣2003 年 61 巻 5 号 p. 454-463
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーSome aspects of green process chemistry are summarized in the context of water (H20) as a key solvent component in the catalytic transformations. We first learn characteristic nature of water and its importance in scalable synthetic operation. Next, emphasis has been placed on such chemical reactions in the presence of PTC catalyst, transition metal catalyst and water itself as a key reagent. The progress will be made in the near future by the utilization of green catalytic reactions with full control of the products and wastes, strongly guided by the statements of Anastas (the 12 principles of green chemistry).抄録全体を表示PDF形式でダウンロード (1592K) -
西脇 正憲2003 年 61 巻 5 号 p. 464-471
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーRecently, green chemistry (GC) plays an important role for manufacturing active pharmaceutical ingredients (APIs) at pharmaceutical companies. For example, large amount of aluminum waste was originally involved and dichloromethane used as a solvent in the process of a new anticholinergic agent, Vamicamide (FK 176), useful for the treatment of urinary incontinence. Non-selective and tedious procedures for alkylation of quinazoline nucleous were used on a laboratory scale in the process of a novel aldose reductase inhibitor, Zenarestat (FK 366) developed for the remedy of diabetic complications. These problems must be excluded before realizing a truly efficient process on a large scale. New process involved much less amount of waste in the case of Vamicamide, and utilized regioselective alkylation reaction for Zenarestat. As a result, E-factor and reaction mass efficiency (RME) were dramatically improved. Herein, we report our efforts leading to an efficient, practical and environmentally friendly process amenable to a large scale synthesis.抄録全体を表示PDF形式でダウンロード (1314K) -
櫃木 啓人, 碇屋 隆雄2003 年 61 巻 5 号 p. 472-483
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーChemical transformations in supercritical fluids (SCFs) have enormous potential advantages. The possibilities of rate enhancement and adjustable selectivities will motivate the research of chemical reactions in SCFs. In addition to the scientific benefits, supercritical carbon dioxide (scCO2) as a reaction medium and reactant possesses economical, technical, and environmental advantages in line with the spirit of the “Green Chemistry”. Recent progress in the organic reactions and organometallic catalysis in scCO2 is reviewed with emphasis on the benefits of utilization of CO2.抄録全体を表示PDF形式でダウンロード (1877K) -
Philip G. Jessop2003 年 61 巻 5 号 p. 484-488
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe combination of scCO2 with a non-volatile liquid such as ionic liquids, water, or poly (ethylene glycol) creates a biphasic mixture suitable for homogeneous catalysis with facile catalyst/product separation and catalyst recycling. Continuous-flow processes are also possible. Dissolution of the CO2 into the nonvolatile liquid during the reaction can have desirable or undesirable effects on the properties of the liquid phase and the reaction performance. Examples of the use of these biphasic systems are described, with an emphasis on systems involving ionic liquids.抄録全体を表示PDF形式でダウンロード (995K) -
松本 謙一郎, 土肥 義治2003 年 61 巻 5 号 p. 489-495
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーIn last half century, petrochemical polymers have been developed, however the high stability of these polymers has led to an increase in the pollution of plastic waste. Biodegradable polymers are one solution to this problem. Polyhydroxyalkanoates (PHA) are a family of polyesters synthesized by microbes and can be used as biodegradable thermoplastics which may substitute for petrochemical polymers. At present, there are two main reasons why PHAs are not used commercially. First, the production cost of PHA is too expensive. Second, the physical properties of PHA are relatively poor compared with those of petrochemical polymers. In order to address these problems, the metabolic pathway of PHA biosynthesis was altered by genetic engineering to improve both physical properties of PHA and efficiency of PHA production. Engineering of PHA polymerase encoding genes has generated mutant PHA polymerases which are capable of higher PHA accumulation. To further address the issue of PHA production costs, transgenic plants harboring PHA biosynthesis genes from bacteria were generated. These transgenic plants have the potential to produce PHA at low cost. Further research in these areas will make the goal of having PHA commercially available, achievable.抄録全体を表示PDF形式でダウンロード (1147K) -
川島 信之2003 年 61 巻 5 号 p. 496-505
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThere is a growing demand for the saving of fossil resources and the reduction of greenhouse gas emissions with the aim of promoting society that is capable of sustainable development. In the area of developing materials as well as in other areas of activities, various efforts are being made for that objective in the aspects of raw materials, manufacturing technology, and disposal of materials after use. Bio-based polymers are attracting attention because of its important role in switching the raw materials from exhaustible resources to annually renewable resources.
Polylactic acid has two characteristics. One is that the raw material lactic acid is produced by fermenting starch and saccharides that are derived from various biomass. The other is polylactic acid is biodegradable slowly in the environment and rapidly in compost.
This paper introduces polylactic acid as bio-based polymers from the perspective of its life cycle contributing to the saving of fossil resources and the reduction of greenhouse gas emissions. This paper also describes a polylactic acid manufacturing process which is typified by ring opening polymerization and direct polycondensation and discusses the issues to be addressed for the growth of the market for the material.抄録全体を表示PDF形式でダウンロード (2482K) -
大橋 武久2003 年 61 巻 5 号 p. 506-516
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe present situation and the development of Japanese green chemistry are discussed.
Subjects to be solved and the strategy to be adopted are discussed. Several examples of industrial biotechnology are described.抄録全体を表示PDF形式でダウンロード (1504K) -
龍野 孝一郎, 中村 哲二2003 年 61 巻 5 号 p. 517-522
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリーThe application of enzymes to an organic synthesis is one of the most useful and practical methods for the production of nitriles, amides and carboxylic acids. There are two different enzymatic pathway for the degradation of nitrile compounds. One is two step degradation involving nitrile hydratase and amidase, via an amide as an intermediate. The other is the direct hydrolysis of nitriles to the corresponding acids and ammonia, catalyzed by nitrilase. Some of the nitrilases are capable of hydrolyzing nitriles stereospecifically. Rhodococcus sp. N-774 was the first strain that was put into commercial use to produce acrylamide from acrylonitrile. Rhodococcus rhodochrous J-1 exhibits a magnitude of order higher productivity than strain N-774. The enzymatic transformation process to produce R-mandelic acid using a R-specific nitrilase has been commercialized by our company. In this article are introduced novel processes for enzymatic production of acrylamide, R-mandelic acid and other compounds.抄録全体を表示PDF形式でダウンロード (953K) -
麻生 眞次, 馬場 俊秀2003 年 61 巻 5 号 p. 523-529
発行日: 2003/05/01
公開日: 2010/01/22
ジャーナル フリーThe carbamic acid esters (carbamates) are prepared by alkoxycarbonylation of 2, 4-tolylenediamine with dimethylcarbonate, diethylcarbonate and di-n-butylcarbonate. Carbamates are obained in good yields (≥90%) using zinc acetate as catalyst. Intermediates in the reactions of carbonates and 2, 4-tolylenediamine to carbamates are 3-amino-4-methyl phenyl carbamates and ureas.
Carbamates are pyrolyzed to tolylenediisocyanate and corresponding alcohols. The difference in isocyanate yields among carbamates prepared from dimethylcarbonate, diethylcarbonate and di-n-butylcarbonate is also discussed.抄録全体を表示PDF形式でダウンロード (926K) -
辻 篤子2003 年 61 巻 5 号 p. 530-531
発行日: 2003/05/01
公開日: 2009/11/13
ジャーナル フリー「おもしろいなあ.だって, グリーンとケミストリーって, ほとんど逆の概念でしょう?」.科学部のある記者が, 「グリーンケミストリー」の話を聞いてこんな感想をもらした.2年前の秋のことだ.さらにその記者は続けて, 「つまりは, 化学のイメージ挽回作戦ですね」.なるほどそういう見方もあるのかと, ちょっと驚いたが, 化学物質による環境汚染や毒性と結びつけて考えられがちな化学のイメージを考えれば, さほどとっぴな見方ではないかもしれないと, 思い直した.この記者は文科系出身, とくに化学にくわしいというわけではなかったが, それだけに, ごく普通の感覚に近いといえるかもしれない.抄録全体を表示PDF形式でダウンロード (344K)
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