Oxidation green chemistry

Campos-Martin, J.M., Capel-Sanchez, M.C., and Fierro, J.L.G. Highly efficient deep desulfurization of fuels by chemical oxidation. Green Chemistry, 2004, 6, 557. 

Keywords Oxidation, green chemistry, heterogeneous, catalysis, hydrogen peroxide... 

Holbrey, J. D. Turner, M. B. Reichert, W. M. Rogers, R. D. (2003). New ionic liquids containing an appended hydroxyl fimctionality from the atom-efficient, one-pot reaction of 1-methylimidazole and acid with propylene oxide. Green Chemistry, Vol. 5, No. 6, pp. 731-736, ISSN 1463-9262. 

Enzyme-mediated oxidation reactions offer highly diverse options for the modification of existing functional groups as well as for the introduction of novel function in chiral catalysis. Biooxidations often enable us to obtain complementary solutions to metal-assisted transformations and organocatalysis and are considered one of the important strategies of green chemistry . 

We have reported a simple, green, bench top, economical and environmentally benign room temperature synthesis of MSe (M=Cd or Zn) nanoparticles using starch, PVA and PVP as passivating agents. The whole process is a redox reaction with selenium acting as the oxidant and MSe as the reduction product. An entire "green" chemistry was explored in this synthetic procedure and it is reproducible. The optical spectroscopy showed that all the particles are blue shifted from the bulk band gap clearly due to quantum confinement. Starch capped CdSe nanoparticles showed the presence of monodispersed spherical... 

J.A. Murphy, Free Radicals in Synthesis Clean Reagents Affording Oxidative or Reductive Termination , Pure and Applied Chemistry, Special Topic Issue on Green Chemistry, 2000, 72(7) 1327. 

Oxidation reactions are frequently used in the production of both bulk and fine chemicals. Review the main differences in the processes usually used in each sector, discussing these differences in terms of the 12 principles of green chemistry. 

Synthesis of metal carbonyl clusters on oxide surfaces (followed by extraction into a solvent and workup) is occasionally a more convenient and efficient method for preparation of a metal carbonyl cluster than conventional solution chemistry. This synthetic strategy offers the green chemistry advantage of minimizing solvent use, as the reaction often occurs in the absence of solvent. 

Seddon, K.R. Stark, A. (2002) Selective Catalytic Oxidation of Benzyl Alcohol and Alkylbenzenes in Ionic Liquids. Green Chemistry, 4(2), 119-123. 

In pursuit of green chemistry, Mr. Clean aqueous H2O2 leaves only water. Thus readily available aqueous 30% H2O2 has been used for oxidation of cyclohexene to adipic acid using a PTC and a noble metal catalyst (Sato, 1998). 

The multi-component systems developed quite recently have allowed the efficient metal-catalyzed stereoselective reactions with synthetic potential [75-77]. Multi-components including a catalyst, a co-reductant, and additives cooperate with each other to construct the catalytic systems for efficient reduction. It is essential that the active catalyst is effectively regenerated by redox interaction with the co-reductant. The selection of the co-reductant is important. The oxidized form of the co-reductant should not interfere with, but assist the reduction reaction or at least, be tolerant under the conditions. Additives, which are considered to contribute to the redox cycle directly, possibly facilitate the electron transfer and liberate the catalyst from the reaction adduct. Co-reductants like Al, Zn, and Mg are used in the catalytic reactions, but from the viewpoint of green chemistry, an electron source should be environmentally harmonious, such as H2. 

Kotani, M., Koike, T., Yamaguchi, K. and Mizuno, N. (2006) Ruthenium hydroxide on magnetite as a magnetically separable heterogeneous catalyst for liquid-phase oxidation and reduction. Green Chemistry, 8 (8), 735-741. 

Oliveira, R.L., Kiyohara, P.K. and Rossi, L.M. (2010) High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols. Green Chemistry, 12 (1), 144-149. 

Amination of aromatic nitro compounds is a very important process in both industry and laboratory. A simple synthesis of 4-aminodiphenyl amine (4-ADPA) has been achieved by utilizing a nucleophilic aromatic substitution. 4-ADPA is a key intermediate in the rubber chemical family of antioxidants. By means of a nucleophibc attack of the anilide anion on a nitrobenzene, a o-complex is formed first, which is then converted into 4-nitrosodiphenylamine and 4-nitrodiphenylamine by intra- and intermolecular oxidation. Catalytic hydrogenation finally affords 4-ADPA. Azobenzene, which is formed as a by-product, can be hydrogenated to aniline and thus recycled into the process. Switching this new atom-economy route allows for a dramatic reduction of chemical waste (Scheme 9.9).73 The United States Environmental Protection Agency gave the Green Chemistry Award for this process in 1998.74... 

Thus, the advanced metal ion-implantation method has opened the way to many innovative possibilities, and the design and development of such unique titanium oxide photocatalysts can also be considered an important breakthrough in the utilization of solar light energy, which will advance research in sustainable green chemistry for a better environment [4,5,15,16,20-22]. 

In continuous processing, the aldehyde product is removed from the reaction before any over-oxidation can occur, offering significant Green Chemistry advantages. This is shown diagramahcally in Scheme 11.6. 

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