Hypochlorite, oxidation

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. 

Oxidized starches, usually those prepared by hypochlorite oxidation, ate used in paper coatings and adhesives (qv) to improved surface characteristics for printing or writing. Oxidized starches may also be employed as textile warp sizes and finishes, in manufacture of insulation and... 

The pH of the chlorine dioxide reaction mixture must be maintained in the 2.8—3.2 pH range, otherwise decreased conversion yields of chlorite to chlorine dioxide are obtained with by-product formation of chlorate. Generator efficiencies of 93% and higher have been demonstrated. A disadvantage of this system is the limited storage life of the sodium hypochlorite oxidant solution. 

Perhaps one of the most exciting developments in the chemistry of quinoxalines and phenazines in recent years originates from the American University of Beirut in Lebanon, where Haddadin and Issidorides first made the observation that benzofuroxans undergo reaction with a variety of alkenic substrates to produce quinoxaline di-AT-oxides in a one-pot reaction which has subsequently become known as the Beirut reaction . Many new reactions tend to fall by the wayside by virtue of the fact that they are experimentally complex or require starting materials which are inaccessible however, in this instance the experimental conditions are straightforward and the starting benzofuroxans are conveniently prepared by hypochlorite oxidation of the corresponding o-nitroanilines or by pyrolysis of o-nitrophenyl azides. 

Acetylation of 2,3 -bithienyl occurs in the 5-position, which is in accordance with considerations on the localization energies, The structure was proved by hypochlorite oxidation followed by Raney nickel desulfurization of the 5-carboxy-2,3 -bithienyl. ... 

Dicarboxylic acids have been prepared by the stepwise acylation and Wolff-Kishner reduction of thiophene or di-2-thienylmethane with ester chlorides of dicarboxylic acids. Another method consists of the AICI3 catalyzed acylation of w-phenylalkylthiophenes which occurs both in the free thiophenic position and in the para position of the ring (226). Hypochlorite oxidation and desulfurization then give diacides such as (227)... 

Early attempts to prepare 5-amino- and 5-acylaminobenzofuroxans by hypochlorite oxidation of the corresponding o-nitroanilines met with failure. Pyrolysis of the appropriate azide, however, gives 5-dimetliylamino- and 5-acetamidobenzofuroxan, whereas urethans of type (33) are produced by Curtius degradation of the 5-carboxylic acid. Controlled hydrolysis of the acetamido compound and the... 

Attempts to prepare 6-hydroxybenzofuroxan by demethylation of 5-methoxybenzofuroxan, by pyrolysis of 4-azido-3-nitrophenol, and by hypochlorite oxidation of 4-amino-3-nitrophenoD failed. This rather unstable compound was finally prepared by hydrolysis of 5-acetoxybenzofuroxan its tautomeric possibilities are numerous, but from the similarity of its ultraviolet spectrum to that of 5-methoxybenzofuroxan it was considered to be largely in the hydroxy form. It is a fairly strong acid, of pK 6.76 (cf. 5-hydroxybenzo-furazan, pK 7.28). 7-Hydroxy-4,6-dinitrobenzofuroxan has been reported as arising from oxidation and nitration of dinitrosoresorcinol monooxime (tetraoxocyclohexene trioxime). ... 

Alkoxybenzofuroxans are weU-known, and the hypochlorite oxidation method is usually used for their preparation. For the formation of haloalkoxybenzofuroxans from nitrobenzofuroxans, see Section VII, B. 

Bicarbonate. Carbonate Chloride.. . Hydrate.. . Hypochlorite. Oxide. Sulfale. . . Sulfate. . . Nitrate. . . I hofl >hate... 

Iodoxybenzene has been prepared by the disproportionation of iodosobenzene,4Hi by oxidation of iodosobenzene with hypo-chlorous add or bleaching powder,7 and by oxidation of iodobenzene with hypochlorous acid or with sodium hydroxide and bromine.8 Other oxidizing agents used with iodobenzene include air,3 chlorine in pyridine,9 Caro s acid,19-11 concentrated chloric acid,15 and peracetic acid solution.13 Hypochlorite oxidation of iodobenzene dichloride has also been employed.14... 

Because hypochlorites oxidize organic material, they are used in liquid household bleaches and as disinfectants. Their action as oxidizing agents stems partly from the decomposition of hypochlorous acid in solution ... 

The stripping of cellulosic materials dyed with reactive dyes is carried out by alkaline reduction followed by hypochlorite oxidation, preceded by a boiling treatment with EDTA if metal-containing dyes have been used. For example, a treatment with 5 gA sodium carbonate or sodium hydroxide and 5g/l sodium dithionite at the boil is followed by a treatment in 0.5-1 °Tw hypochlorite, an antichlor and thorough rinsing. 

Cyclic ADC compounds are similarly prepared by oxidation of the corresponding cyclic hydrazine derivatives. The most commonly encountered compounds are the 3//-l,2,4-triazole-3,5(4//)-diones (5), and in particular the 4-phenyl derivative (5, R = Ph), usually abbreviated as PTAD. Similarly, the abbreviation MTAD is used for the 4-methyl derivative. First prepared by Thiele,18 PTAD remained unused in organic synthesis until Cookson reported its powerful dienophilic properties some 70 years later.19 PTAD is an isolable, red, crystalline compound, prepared by r-butyl hypochlorite oxidation of 4-phenylurazole.20 Other oxidants which have been successfully... 

Benzofurazan oxide has also been prepared by the oxidation of o-nitroaniline with phenyl iodosoacetate.6 Other methods of preparation are given in reference 4. The hypochlorite oxidation method has been used in the synthesis of various substituted benzofurazan oxides.6... 

The separation of technetiiun from ruthenium involves major difficulties due to the presence of a large number of oxidation states and ionic forms of ruthenium, some of which are capable of being extrated with technetiiun. However, the separation is accomplished by the extraction of pertechnetate with pyridine in 4 N NaOH In alkaline media ruthenium is reduced by the organic solvent to lower valences and is not extracted. The extraction of ruthenium from the aqueous phase can be achieved only in the presence of an oxidant in the solution (e.g. a hypochlorite oxidizing to RuOj which is extracted with pyridine). 

S. Wolf, S. K. Hasan, J. R. Campbel, Ruthenium Trichloride-Catalysed Hypochlorite Oxidation of Organic Compounds, Chem. Commun. 21 (1970) 1420—1421. 

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. ... 

Hydrazine was isolated first as a sulfate salt by Curtius in 1887. Earlier, in 1875, Fischer prepared and identified the organic derivatives of hydrazine. Raschig in 1906 prepared hydrazine by hypochlorite oxidation of ammonia. 

Diloxanide was first prepared by the reaction of 4-hydroxy-A-methyl aniline with sodium cyanide and chloral hydrate in the presence of a base [9]. Furoic acid was prepared by the hypochlorite oxidation of... 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

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... 

---