Oxidation with Sodium Hypochlorite

To a solution of 1.0 g (0.048 mol) of benzalacetophenone in 7.5 mL of pyridine is added 11 mL of a fresh 5.25% solution of sodium hypochlorite (Clorox). An exothermic reaction is accompanied by the almost immediate fading of the yellow color of the solution. When the inixtur becomes almost colorless, 25 mL of water is added. The precipitated whiteVystals of the epoxide are filtered with suction, washed thoroughly with water, and recrystallized from ethanol to give 1.0 g (94%) of l,3-diphenyl-2,3-epoxy-l-propanone, mp 89-90 °C. 

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Oxidation of methyl perfluoroalkyl sulphones with refluxing aqueous potassium permanganate produced the perfluorinated alkanesulphonic acid in 85% yield as the potassium salt (equation 86). On the other hand, attempted oxidation with sodium hypochlorite caused only chlorine substitution (equation 87). Reaction of the new sulphone with aqueous hydroxide gave the same perfluoroalkane sulphonic acid salt (equation 88). 

Oxidized starch, usually oxidized with sodium hypochlorite, is whiter than unmodified starch it has increased clarity and lower viscosity. 

Intramolecular nitrile oxide—olefin cycloaddition of oxazolidine and thiazoli-dine oximes 407 (R = H, Me R1 =H, Me X = 0, S n = 1,2) proceed stereose-lectively, yielding tricyclic fused pyrrolidines and piperidines. Thus, 407 (n =2 R = H R1 =Me X=S) has been oxidized to the nitrile oxides with sodium hypochlorite, in the presence of triethylamine in methylene chloride, to give the isoxazolothiazolopyridine 408 in 68% yield. Reduction of 408 with lithium aluminum hydride affords mercaptomethylmethylpiperidine 409 in 24% yield (448). 

Accent [Aqueous carbon compound effluent treatment] A process for oxidizing organic contaminants in aqueous streams by catalyzed oxidation with sodium hypochlorite. The catalyst is promoted nickel oxide, which retains active oxygen at its surface, as well as adsorbing the organics. Developed by ICI Katalco and first offered in 1998. 

The acid, referred to as tetra acid , is prepared as follows In a Friedel-Crafts reaction, acenaphthene 72 is reacted with malonic dinitrile and aluminum chloride. The resulting condensation product 75 is oxidized with sodium chlorate/hy-drochloric acid to form the dichloroacenaphthindandione 76. Oxidation with sodium hypochlorite solution/sodium permanganate affords naphthalene tetracar-boxylic acid 68, mostly existing as the monoanhydride 68a. The dianhydride, on the other hand, evolves only after drying at approx. 150°C. 

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],... 

L-fhreo-Pentos-2-ulose (9) was prepared by several procedures (see Scheme 3). In procedure A, D-galacturonic acid (14) was reduced with sodium amalgam to L-galactonic acid (15), which lactonized to L-ga-lactono-1,4-lactone (16) by removal of water. Treatment of 16 with ammonia in methanol afforded L-galactonamide (17) which, on oxidation with sodium hypochlorite, gave L-lyxose (18). Reaction of 18 with phenylhydrazine yielded the corresponding osazone (19) which, on hydrolysis, afforded 9. 

Dicarboxyl starch can also be made by oxidation with sodium hypochlorite or hypobromite (see reference 116). Reaction with hypochlorite is accelerated by use of catalytic amounts of sodium bromide.123,124... 

Aminobenzimidazoles and 2-aminobenzothiazoles can be oxidized with sodium hypochlorite to afford the corresponding 2,2-azo compounds. A rather unusual autooxidation of a heteroaromatic (7-amino group occurs on treatment of l-benzyl-2-aminobenzimidazole 671 with excess sodium or potassium in liquid ammonia. The products are 2,2-azobenzimidazole 674 and 2-nitrobenzimidazole 675, formed in 60 and 40% yields, respectively. It is supposed that... 

Since 1966 hexanitrostilbene (HNS) and since 1978 triaminotrinitrobenzene (TATB) are produced commercially (Fig. 1.3). Both secondary explosives show excellent thermal stabilities and are therefore of great interest for the NAVY (fuel fires) and for hot deep oil drilling applications (Fig. 1.3). Especially HNS is known as a heat- and radiation-resistant explosive which is used in heat-resistant explosives in the oil industry. The brisance of HNS is lower than that of RDX, but the melting point of approx. 320 °C is much higher. HNS can directly be prepared from trinitrotoluene through oxidation with sodium hypochlorite in a methanol/THF solution ... 

Remarks. The condensation of the sulfo derivative of p-nitrotoluene was first observed accidentally by Johann Walther, and further investigation of the reaction has shown that different dyes, varying in color from yellow to red, are formed depending on the nature of the reaction. If the condensation is carried out under somewhat more drastic conditions, for example, with more sodium hydroxide and at a liigher temperature, the color of the dye is more greenish. Still more greenish dyes can be obtained by careful oxidation with sodium hypochlorite (sun yellow 3G, polyphenyl yellow 3G). 

Various types of dyes are prepared from dehydrothiotoluidine. The free base or its sulfonic acid is diazotized and coupled with various naph-tholsulfonic acids such as, for example, e acid (l-naphthol-3,8-disul-fonic acid). The resulting dye is characterized by its high purity of color and can be discharged to a pure white. Such red direct dyes are sold under various names, and are usually referred to as dyes of the erika red type. (Erika Z is the combination from dehydxothioxylidine and e acid. l-Naphthol-3,6-disulfonic acid gives a very similar dye.) In addition to the true azo dyes from dehydrothiotoluidine, two other products are made which are important yellow dyes. One of these dyes is the naphthamine yellow NN (also called chloramine yellow) (Kalle), formed from dehydrothiotoluidinesulfonic acid by oxidation with sodium hypochlorite. The other is thiazole yellow or Clayton yellow, which is made by combining the diazo compound of dehydrothiotoluidinesulfonic acid with a second molecule of the same compound to form a diazoamino compound. 

Nitriles are also the usual products of oxidation of aliphatic amines RCH2NH2 by nickel peroxide and lead(IV) acetate. Aliphatic azo compounds can be prepared from these primary amines by first converting them into ulfamides (6), these then being oxidized with sodium hypochlorite or (better) r butyl hypochlorite (Scheme 9). A few aliphatic azo compounds can be formed in good yield by direct oxidation of r-alkylamines for example, AIBN was formed (86%) by oxidation of the amine Me2C(CN)NH2 with sodium hypochlorite. A special case of azoalkane foimation is the synthesis of chlorodiazirines (7) from amidines RC(= NH)NH2 by oxidation with sodium hypochlorite. ... 

For a long time, the Raschig process, which was discovered in 1907, was used for the production of hydrazine. Here, ammonia is oxidized with sodium hypochlorite in alkahne solution (pH = 8 11). In the initial rapid reaction, (55) sodium hypochlorite reacts with ammonia, forming chloramine. Chloramine then reacts with ammonia in a slower second reaction. ... 

The production of hydrazine from urea by treatment with sodium hypochlorite is no longer used. Here urea was oxidized with sodium hypochlorite followed by hydrolysis and decarboxylation to yield hydrazine. 

The primary hydroxyl group in 2,3 4,6-diisopropylidene-L-sorbose was oxidized with sodium hypochlorite in the presence of NiCls by Weijlard, who obtained a 90% yield of 2,3 4,6-diisopropylidene-2-keto-L-gulonic acid monohydrate. This reaction is normally carried out with permanganate for the production of ascorbic acid, but a wartime shortage of this oxidant caused the consideration of chlorine as a substitute. Similar results were found by Beer and Preobrazhenskii in more concentrated solutions. The yield of product was lowered drastically when the concentration of sodium hydroxide was less than 30%, when the chlorine-sorbose molar ratio was less than 4.1 and when... 

In the Raschig process, ammonia is oxidized with sodium hypochlorite ... 

The allene moiety in penta-3,4-dien-l-ol has been successfully dicyclopropanated with an excess of trimethylaluminum/diiodomethane in dichloromethane at room temperature. The spiropentylethanol 35 obtained gives spiropentaneacetic acid on oxidation with sodium hypochlorite, which is a new dehydrogenase inhibitor used as a model in biological studies. 

Oxidation with sodium hypochlorite converts phthalimide into anthranilic acid, (11),... 

The pyrrolinyl- (6-11) and pyrrolyl-substituted (12-13) eudistomin skeletons were first prepared by Rinehart from 1-cyano-P-carboline (145), which can be obtained from the corresponding acid (28). Grignard reaction with appropriately protected 3-bromopropanal (Scheme 4) provided the necessary carbons with appropriate oxidation level for cyclization to either of these ring systems. The pyrrolyl-substituted eudistomins then result upon hydrolysis of the imine and acetal functions with concomitant cyclization in the presence of ammonia. The pyrrolinyl-eudistomins require reduction of the imine to the amine followed by acetal hydrolysis and simultaneous ring closure to isomer 147. Reduction of the imine 147 followed by allylic oxidation with sodium hypochlorite isomerizes 147 to the pyrrolinyl-eudistomin skeleton (149). 

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