Alkaline hypochlorite

When treated with alkaline hypochlorite solution anthranilic acid is obtained. This reaction, the first stage in the indigo synthesis, is the most important commercial outlet for phthalimide. 

The reactivity of the amino radical has not yet been investigated. Alkaline hypochlorite oxidation, known in the pyridine series to yield azo derivatives (155,156). and photolysis of N,N-dichloro derivatives, which may be obtained by action of sodium hypochlorite on amino derivatives in acidic medium (157). should provide interesting insight on this reactivitv. 

Other Cellulosics. Rayon is bleached similarly to cotton but under milder conditions since the fibers are more easily damaged and since there is less colored material to bleach. Cellulose acetate and triacetate are not usually bleached. They can be bleached like rayon, except a slightly lower pH is used to prevent hydrolysis. The above fibers are most commonly bleached with hydrogen peroxide. Linen, dax, and jute requite more bleaching and mil der conditions than cotton, so multiple steps are usually used. Commonly an acidic or neutral hypochlorite solution is followed by alkaline hypochlorite, peroxide, chlorite, or permanganate, or a chlorite step is done between two peroxide steps. A one-step process with sodium chlorite and hydrogen peroxide is also used. 

Saturated hydrocarbons can be chlorinated in moderate yields under mild conditions in a biphasic system consisting of alkaline hypochlorite solution and CH2CI2 containing Ni(Il) bis(saHcyHdene)ethylenediamine as chlorination catalyst and bexadecyltrimetbylammonium bromide as phase-transfer catalyst (166). 

Compared to its precursor (HNCO), CA is unusually stable to hydrolysis. It is only slowly hydroly2ed by hot aqueous alkaU and virtually iuert to acidic hydrolysis. Indeed, CA can be heated under pressure iu sulfuric acid solution at 200°C with minimal decomposition. The tria2iae ring, however, can be cleaved by alkaline hypochlorite forming N2 and HCO3 (17). 

The oxidation of o-nitroanilines to benzofuroxans was discovered by Green and Rowe, who used alkaline hypochlorite. Although this method has been used extensively, it occasionally fails to... 

Ruthenium and osmium are decidedly less noble than the other four metals of the platinum group. Both exist in numerous valency states and very readily form complexes. Ruthenium is not attacked by water or non-complexing acids, but is easily corroded by oxidising alkaline solutions, such as peroxides and alkaline hypochlorites. 

Hydrazine, NH2NH2, is an oily, colorless liquid. It is prepared by the gentle oxidation of ammonia with alkaline hypochlorite solution ... 

An alkaline hypochlorite was used to carry out the following reaction ... 

A mixture of alkaline hypochlorite/formic acid, which is used when treating certain industrial residues, detonates at 55°C. 

Some reagents are milder and less powerful oxidants and have been used to oxidize arylamines to the corresponding nitroso compounds. These include 30 % hydrogen peroxide in acetic acid, ° aqueous solutions of potassium permanganate, and alkaline hypochlorite amongst others. The hypochlorite oxidation of arylamines containing o-nitro substiffients is reported to yield benzofuroxans. For a discussion of the synthesis of aromatic nitroso compounds the readers are directed to a review by Boyer. ... 

Benzofuroxans are far more stable than simple furoxans and are more favourable for practical applications. There are two standard methods for the synthesis of the benzofuroxan skeleton (1) treating an ortho-nitroarylamine with a mild oxidant like sodium hypochlorite and (2) either heating or irradiating an orf/to-nitroarylazide with UV light. Benzofuroxan itself has also been prepared by treating 1,2-benzoquinone dioxime with alkaline hypochlorite or alkaline potassium ferricyanide solution. ... 

Oxidation of aminopyridines with Caro s acid gives nitropyridines the use of peroxy-trifluoroacetic acid leads to nitropyridine JV-oxides (60JOC1716). Oxidation with alkaline hypochlorite converts aminopyridines into symmetrical azopyridines, and azoxypyridines are formed by oxidation with persulfate (59YZ549). 

Methyl />-ethylbenzoate was prepared from ethylbenzene (1 kg.), which was converted into jb-ethylacetophenone by adding aluminum chloride (792 g.), followed by acetyl chloride (462 g.), which was added with stirring at 0-5° over a period of 3 hours. The mixture was stirred for 1 hour longer, allowed to stand overnight, and washed with iced dilute hydrochloric acid. The ethylbenzene was removed by distillation, and the crude product was oxidized to p-ethylbenzoic acid with alkaline hypochlorite.4 Recrystallization of the crude acid from 95% ethanol yielded 350 g. (41%) of the pure acid m.p. 110-112°. Esterification with methanol in the presence of hydrogen chloride 4 yielded methyl />-ethylbenzoate (77-79%). 

The oxidation of JV,7V -dialkylthioureas to the corresponding carbodiimides can also be accomplished in excellent yields by alkaline hypochlorites below 0°C [15, 16, 62-64], The use of excess hypochlorite converts the sulfur into sulfate ion. This process has the main advantage of using inexpensive reagents and thus can be applied to the large-scale production of carbodiimides (Eq. 20). 

Hydrolysis of tosylhydrazones has been achieved by treatment with alkaline hypochlorite [61]. This allylic activation ensures the sp1 hybridized carbon behave as an avid acceptor. 

Oxidized Starches. Alkaline hypochlorite treatment introduces carboxyl and carbonyl groups, effects some depolymerization, and produces whiter (bleached) products that produce softer, clearer gels. Ammonium persulfate is used in some paper mills with continuous thermal cookers to prepare in situ bigb solids, low viscosity dispersions. Most of the hypochlorite-oxidized starch and all the ammonium persulfate-oxidized starch is used in the paper industry. The low solution viscosity and good binding and adhesive properties of these products make them especially effective in high solids, pigmented... 

Hypochlorite sweetening the oxidation of mercaptans in a sour stock by agitation with aqueous, alkaline hypochlorite solution used where avoidance of free-sulfur addition is desired, because of a stringent copper strip requirements and minimum expense is not the primary object. 

The mixture of methotrexate sodium with cytarabine, fluorouracil, hydrocortisone sodium, and prednisolone sodium phosphate produces precipitate upon storage, although it is not observed immediately. A concentration-dependent photodegradation was reported for methotrexate and considered high in the presence of bicarbonate ions and unprotected polybutadiene tubings.226 Methotrexate wastes may be disposed of by oxidation with potassium permanganate and sulfuric acid or by oxidation with aqueous alkaline hypochlorite. 

The alkaline hypochlorite solution is maintained at 25 to 30° while 25 g. of pulverized iron(III) nitrate 9-hydrate (0.06 mol) is added in small portions over a period of 45 minutes to 1 hour. Sodium hydroxide is added to the solution until saturation is reached during this operation the temperature is maintained at 30°. The mixture is then fil- University of Kentucky, Lexington, Ky. f Pennsylvania State College, State College, Pa. t University of Illinois, Urbana, 111. 

Arylfurazancarboxamides on treatment with alkaline hypochlorite undergo Hofmann degradation to the amines likewise carbamates result from Curtius rearrangement of furazanylacyl azides in the presence of alcohols. 

Heating o-nitrosophenols with hydroxylamine is reported to give furazans, naphtho[l,2-c]furazan (95) being formed from both l-nitroso-2-naphthol and 2-nitroso-l-naphthol, presumably by oximation of the tautomeric o-naphthoquinone monooximes and subsequent dehydration. Compound (95) has also been prepared by oxidation, using alkaline ferri-cyanide or hypochlorite, of l-amino-2-nitroso- and 2-amino-l-nitroso-naphthalene. This latter approach is suitable for heterocyclic fused furazans thus 4,6-diamino-5-nitrosopyrimidine is converted into the furazanopyrimidine (96) by oxidation with lead tetraacetate (71JOC3211). In a similar reaction alkaline hypochlorite oxidizes o-nitrosoacetaniiide to benzofurazan in quantitative yield. 

Direct dehydrogenation of oximes is also possible, particularly for sterically hindered nitrile oxides. The most successful oxidizing agents are alkaline hypobromite and NBS in the presence of base, the latter being valuable when basic groups are present. Lead tetraacetate and alkaline hypochlorite have also been employed, but the yields are lower. The formation of furoxans from the reaction of alkoximes with nitrogen oxides is believed to proceed via the corresponding nitrolic acids. 

Thioureas as are also oxidized with excess alkaline hypochlorite below 0 °C to give carbodiimides 24 in excellent yields." ... 

Hydrolysis—Hydrolyzing agents Alkaline hypochlorite is effective for hydrolyzing VX and G agents (for further information, see Table 26.3). 

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