Sodium hypochlorite, as an oxidizing

Interesting results were obtained in the asymmetric epoxidation of the (Z)-alkenes 94 using the (salen)Mn catalyst 95 in conjunction with sodium hypochlorite as an oxidant, giving the optically active -epoxides 96 as the major products,1711 as... 

Sodium hypochlorite is an effective, inexpensive, and nontoxic oxidant. Zhang and coworkers [23] have prepared a hexaalkylguanidinum-based ionic hquid and apphed it as both a phase transfer catalyst (PTC) and solvent in the biphasic oxidation of substituted benzyl alcohols using sodium hypochlorite as an oxidant (Scheme 14.24). 

Attempts have been made to exploit the intrinsic C2 symmetry of the phenolate-based dinickel core in enantioselective catalytic reactions. Therefore, enantiomerically pure C2-symmetric ligands such as (736a) and the corresponding dinickel systems (736b) have been prepared ( Equation (27)),1890 and (736b) was tested in the epoxidation of unfunctionalized alkenes with sodium hypochlorite as the oxidant. The catalytic reaction was found to be highly pH dependent with an optimum at a pH of 9. While the complex is catalytically active, significant enantioselectivity was not achieved. 

Hydrazine is produced by the oxidation of ammonia using the Rashig process. Sodium hypochlorite is the oxidizing agent and yields chloramine NH2CI as an intermediate. Chloramine further reacts with ammonia producing hydrazine ... 

As indicated above (Ohme and Schmitz [38a, p. 339]) primary amines converted into the alkylamides of sulfuric acid can be oxidized with sodium hypochlorite to azo compounds. The reaction appears to proceed by way of an intermediate hydrazine, which is ultimately oxidized [38a], The reaction is suitable for the formation of symmetrically substituted azoalkanes. Highly branched primary aliphatic amines have been oxidized with sodium hypochlorite in an aqueous dioxane medium [77],... 

Hypochlorite. Sodium hypochlorite, [CAS 7681-52-9], NaOCl, commonly in solution by (1) electrolysis of sodium chloride solution under proper conditions. (2) reaction of calcium hypochlorite suspension in water and sodium carbonate solution, and then filtering. Used (1) as a bleaching agent fa textiles and paper pulp. (2) as a disinfectant, especially fa water. (3) as an oxidizing reagent. 

The very common TEMPO-mediated Anelli s protocol for the oxidation of alcohols, involving a biphasic CH2Cl2-water mixture containing catalytic TEMPO, or an analogue thereof, and sodium hypochlorite as a secondary oxidant, shows a great selectivity for the oxidation of primary alcohols in the presence of secondary ones9 and has found some use in Synthetic Organic Chemistry.10... 

The asymmetric oxidation of indene to the corresponding epoxide (Equation 24) is carried out commercially by Sepracor on a small scale. Chiral indene oxide is an intermediate in the synthesis of crixivan (an HIV protease inhibitor). Reaction is carried out at 5°C with moderately high turnover numbers in the presence of an exotic donor ligand ( P3NO , 3-phenylpropylpyridine N oxide) and sodium hypochlorite as the terminal oxidant. A similar epoxidation of a simple cis olefin (Equation 25) leads to an enantiomerically pure amino-alcohol used in the synthesis of taxol, a potent anticancer drug. 

In their speed of reaction with the halogens, in acid or in alkaline solutions, the simple sugars may be divided into two main classes, the aldoses and the ketoses. The oxidation of the former is very rapid compared with that of the latter. Kiliani showed that when D-glucose and D-fructose were each treated with an equal weight of bromine in water, the ketose required 350-500 hours for completion of the oxidation, in contrast to two to three hours for the aldose. The same difference exists in buffered solutions Honig and Ruzicka found that the rates were two hours and five minutes, respectively. In alkaline solution under controlled conditions, the aldoses can be quantitatively oxidized with sodium hypoiodite in the presence of D-fructose or L-sorbose without appreciable attack on the ketoses. Ochi reported a similar but less clear-cut difference with calcium hypochlorite as the oxidant. Chlorous acid attacks only the aldoses, leaving the ketoses unaltered. The same effect was noted with the keto acids Kiliani reported that 2-keto-L-rhamnonic acid was stable to the action of bromine water. A little preliminary work has been done with iodic acid by Williams and Woods who found that D-fructose was oxidized more rapidly than the aldoses. No confirmation of this work has appeared. 

A further oxidation is then performed to establish the carboxylic acid moiety at C-1, which will form the macrolactone later in the synthesis. Sodium chlorite is commonly used as an oxidizing agent and is often applied for saturated and aromatic aldehydes. Hypochloric acid (HOCl) and sodium hypochlorite (NaOCl) are formed as byproducts and have to be destroyed before they can attack the substrate or the product, because they are stronger oxidizing agents. In this case, 2-methyl-2-butene (43) is added to the reaction mixture forming a chlorohydrin 44. 

Sodium hypochlorite, as in household bleach, is an inexpensive oxidant. In use, it does produce by-product... 

The oxide can be used catalytically for the same purpose in presence of H202 or CIO3. Ruthenium tetraoxide reacts more vigorously with organic substances but also has some uses as an oxidant 5 a convenient catalytic method uses RuC13 in sodium hypochlorite solutions.6 Both Ru04 and 0s04 are soluble in alkali hydroxide solutions, but the... 

PbO. Lead peroxide is used as an oxidizing agent in conjunction ivith acetic, sulfuric, or hydrochloric acids, usually the first. One mole yields one atom of oxygen, and a salt of the acid is formed during the process. It must be used in a finely divided form and, for this reason, is best prepared by precipitation rom a solution of lead nitrate by the addition of sodium hypochlorite or bleaching powder. ... 

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