Oxidation of chlorobenzene

Sedlak DL, AW Andren (1991) Oxidation of chlorobenzene with Fenton s reagent. Environ Sci Technol 25 777-782. 

Proposed reaction pathway for oxidation of chlorobenzene with Fenton s reagent. (From Sedlak, D.L. and Andren, A.W., Environ. Sci. Technol., 25, 777-782, 1991a. With permission.)... 

Matthews RW (1980) The radiation chemistry of the terephthalate dosimeter. Radiat Res 83 27-41 Merga G, Schuchmann H-P, Rao BSM, von Sonntag C (1996) OH-Radical-induced oxidation of chlorobenzene in aqueous solution in the absence and presence of oxygen. J Chem Soc Perkin Trans 2 1097-1103... 

Advantageous use of homochiral cyclohexadiene-cis-l,2-diol, available by means of biocatalytic oxidation of chlorobenzene with toluene dioxygenase, has enabled the synthesis of all four enantiomerically pure C18-sphingosines (Nugent, 1998), which are known inhibitors of protein kinase C and important in cellular response mediation for tumor promoters and growth factors. The four requisite diastere-omers of azido alcohol precursors were accessed by regioselective opening of epoxides with either azide or halide ions. 

T. Hudlicky, H. Luna, J. D. Price, and F. Rulin, An enantiodivergent approach to d- and L-erythrose via microbial oxidation of chlorobenzene, Tetrahedron Lett. 1989,... 

Fig. 5 Oxidation of chlorobenzene by Fenton reagent (excess H2O2). Initial conditions [chlorobenzene] = 1.6 mM [Fe2+] = 5.0 mM pH 3.0 [64]...

Synthetic Organic Micropollutants. Micropollutants that frequently presented in water include chlorobenzenes, PAHs, polychlorinated biphenyls (PCBs), and pesticides. Polycyclic aromatic hydrocarbons can be degraded effectively by ozone. But oxidation of chlorobenzenes and PCBs is slow by molecular ozone. However, they are more reactive with hydroxyl radicals. Therefore, it is recommended that either ozonation be conducted at high pH or advanced oxidation processes (AOP) be used. As for the pesticides, their removal by ozonation may be related to their water solubility. However, faster degradations are usually obtained with AOP. ... 

In Banwell s de novo synthesis of Neu5Ac [136] cis-1,2-dihydrocatechol 228, a product of microbial oxidation of chlorobenzene, has been converted into a protected form of Neu5Ac via a fifteen steps reaction sequence (Scheme 50). Synthesis started from azido alcohol 229, obtained from catechol 228 by an established procedure [137]. This was subjected to ozonolytic cleavage and a reductive work-up to afford diol 230. Protection-deprotection reaction sequence led to alcohol 232 which was then oxidized to D-mannosamine derivative 233 using the Swem protocol. Condensation with the organozinc reagent derived from... 

The c/s-dihydroxylation reaction catalyzed by these dioxygenases is typically highly enantioselective (often >98% ee) and, as a result, has proven particularly useful as a source of chiral synthetic intermediates (2,4). Chiral cis-dihydrodiols have been made available commercially and a practical laboratory procedure for the oxidation of chlorobenzene to IS, 2S)-3-chlorocyclohexa-3,5-diene-l,2-c diol by a mutant strain of Pseudomonas putida has been published (6). Transformation with whole cells can be achieved either by mutant strains that lack the second enzyme in the aromatic catabolic pathway, cw-dihydrodiol dehydrogenase (E.C. 1.3.1.19), or by recombinant strains expressing the cloned dioxygenase. This biocatalytic process is scalable, and has been used to synthesize polymer precursors such as 3-hydroxyphenylacetylene, an intermediate in the production of acetylene-terminated resins (7). A synthesis of polyphenylene was developed by ICI whereby ftie product of enzymatic benzene dioxygenation, c/s-cyclohexa-3,5-diene-1,2-diol, was acetylated and polymerized as shown in Scheme 2 (8). 

Catalytic combustion of chlorinated organic compounds overcomes these drawbacks. First, it permeates much lower temperatures and total oxidation of the toxic by-products. Second, it can treat efficiently very dilute pollutants (<1%) that cannot be thermally combusted [57], The oxidation of chlorobenzene over manganese mixed oxides is one example. When manganese was coupled with titania, total conversions were reported at temperatures as low as 400 °C. Differently to platinum [58] where polychlorinated benzenes are still produced. 

Figure 18.11 Influence of water over the total oxidation of chlorobenzene on LaMn03+ (1% H2O, 15% O2 in He) (a) and on the conversion of 1000 ppm of chlorobenzene (15% O2 in He). (Reprinted with permission from [8]. Copyright 1999, Elsevier.)...

Giraudon, J.M., Elhachimi, A., and Leclercq, G. (2008) Catalytic oxidation of chlorobenzene over Pd/perovskites. Appl. 

Tian W, Fan X, Yang H, Zhang X. Preparation of Mn0x/Ti02 Composites and their Properties for Catalytic Oxidation of Chlorobenzene. J Hazard Mater 2010 177 887-891. 

Giraudon J, Elhachimi A, Leclercq G. Catalytic Oxidation of Chlorobenzene over Pd/Perovskites. A/ / / Catal B Environ 2008 84 251-261. 

The influence of the platinum content and/or the number of accessible platinum atoms per gram of catalyst (nPt) was studied in the oxidation of chlorobenzene at different temperatures (250-350°C) on a series of PtHFAU(5) catalysts (Table 5.1). The CO2 yield reported after four hours of reaction, increased simultaneously with increasing temperature and the amount of platinum deposited on the zeolite (Fig. 5.5). 

According to the literature, the platinum state does not seem to be a key factor for the catalytic oxidation of chlorobenzene. Certain studies have used platinum in a reduced state and others have used platinum in its oxidised state. However, studies carried out on the oxidation of VOCs showed that reduced Pt (Pt ) deposited on zeoUtes was the most active species for the oxidation of aromatic hydrocarbons and ketones. " In this context, the l.l%PtHFAU(5) catalyst formerly reduced in situ under hydrogen for six hours at 450°C was tested in the oxidation of chlorobenzene at 300°C. The particular effect of this treatment was to slightly increase the total conversion of chlorobenzene but with a much higher number of polychlorinated compounds (from 6.3 to 33.8 ppm) and amount of coke deposited on the catalyst after reaction (from 0.4 to 1.17%) (Table 5.2). 

Taralunga, M., Mijoin, J. and Magnoux, P. (2005). Catalytic destruction of chlorinated POPs — Catalytic oxidation of chlorobenzene over PtHFAU catalysts, Appl. Catal. B Environ., 60, pp. 163-171. 

Matthews R.W. Photocatal54ic oxidation of chlorobenzene in aqueous suspensions of titanium-dioxide. J. Catal. 1986 97 565-568... 

A multistep synthesis of (+)-kifunensine 37, a potent glycosidase inhibitor, starting from microbial oxidation of chlorobenzene has been rqrarted. ... 

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