Chloramine oxidations with

For the preparation of the parent substance, cyclic diazomethane (67), formaldehyde, chloramine, and ammonia were reacted. Diaziri-dine formation was successful in about 20% yield the diaziridine condensed with further formaldehyde to high molecular weight products the diaziridine detected by its oxidizing power was nonvolatile. Oxidation with dichromate in dilute sulfuric acid led to gaseous diazirine (67) [Eq. (56)]. It was only investigated in solution. 

Nonhalogenated carboxylic acids are also common DBPs from chlorine, chloramines, ozone, and chlorine dioxide [10]. In addition to halogenation reactions that can occur (primarily with chlorine and chloramine), oxidation reactions also occur, and can produce carboxylic acids. There is generally not a concern for toxicity for them, as many are naturally present in foods. 

Carbinolamines, 87 Carbodiimides, 205-222 reaction with alcohols, 170 Carbon monoxide, as reducing agent, 336 a-Carbonyl azo compounds, 324, 326 Caro s add (permonosulfuric add), 408 oxidation with, 409 preparation of, 409 Chloramine T, 377 Chloroacetylenes 120-122 4-Chloro-l, 2-butadiene, 33 Chlorocyclohexenyl acetylene, 121 1 -Chloro-2-JV,N-diphenylaminoacetylene, 128-129... 

Method B Sample was oxidized with chloramine T, reacted with m-aminophenol and the absorbance was measured at 420 nm. 

Regarding ozonation processes, the treatment with ozone leads to halogen-free oxygenated compounds (except when bromide is present), mostly aldehydes, carboxylic acids, ketoacids, ketones, etc. [189]. The evolution of analytical techniques and their combined use have allowed some researchers to identify new ozone by-products. This is the case of the work of Richardson et al. [189,190] who combined mass spectrometry and infrared spectroscopy together with derivatization methods. These authors found numerous aldehydes, ketones, dicarbonyl compounds, carboxylic acids, aldo and keto acids, and nitriles from the ozonation of Mississippi River water with 2.7-3 mg L 1 of TOC and pH about 7.5. They also identified by-products from ozonated-chlorinated (with chlorine and chloramine) water. In these cases, they found haloalkanes, haloalkenes, halo aldehydes, haloketones, haloacids, brominated compounds due to the presence of bromide ion, etc. They observed a lower formation of halocompounds formed after ozone-chlorine or chloramine oxidations than after single chlorination or chlorami-nation, showing the beneficial effect of preozonation. 

Other methods were developed for various anions. Bromides were oxidized with permanganate and the bromine so produced reacted with cyclohexene to form 1,2-dibromocyclohexane [577]. Similarly, iodides were analysed in milk as monoiodoacetone after oxidation with iodate and after reaction of the released iodine with acetone [578]. Pennington [579] utilized the same oxidation reaction for the analysis of iodates the iodine released was analysed as such. Cyanides were chlorinated prior to analysis with chloramine-T and the cyanogen chloride so produced was subjected to GC [580]. Analogously, cyanides and isocyanates form cyanogen bromide with bromine water, which can be analysed by GC [581]. 

The other amino acid residue present in proteins that is susceptible to oxidation is the indole moiety of tryptophan (Fig. 11). The reducing potential of tryptophan is considerably less than that of cysteine and methionine, so oxidation of tryptophanyl residues usually does not occur until all exposed thiol residues are oxidized. Also, the spontaneous oxidation of tryptophanyl residues in proteins is much less probable than that of cysteinyl and methionyl residues. Tryptophan residues are the only chromophoric moieties in proteins which can be photooxi-dized to tryptophanyl radicals by solar UV radiation, even by wavelengths as long as 305 nm (B12). Tryptophanyl residues readily react with all reactive oxygen species, hypochlorite, peroxynitrite, and chloramines. Oxidative modifications of other amino acid residues require use of strong oxidants, which eventually are produced in the cells. Detailed mechanisms of action of these oxidants is described in subsequent sections of this chapter. 

Reaction of 199 and its A-oxide with chloramine leads to the introduction of an amino group on the 1-nitrogen. Treatment of these... 

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. 

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. ... 

Consider the formation of the nitrate ion. The oxidation state of nitrogen in the nitrate ion is +5. Thus, this ion would not be formed from ammonia, because this would need the abstraction of eight electrons. If it is formed from the monochloramine, it would need the abstraction of six electrons, and if formed from the dichloramine, it would need the abstraction of four electrons. Thus, in the chloramine reactions with HOCl, the nitrate is formed from the dichloramine. We will, however, compare which formation forms first from the dichloramine trichloramine or the nitrate ion. The oxidation state of the nitrogen atom in trichloramine is -i-3. Thus, to form the trichloramine, two electrons need to be abstracted from the nitrogen atom. This may be compared to the abstraction of four electrons from the nitrogen atom to form the nitrate ion. Therefore, the trichloramine forms first before the nitrate ion does. 

Arsenoxides and cyanides give rise to acids on oxidation, and aryldi-chloroarsincs may also be converted to acids by the action of hydrogen peroxitle in glacial acetic acid, or by oxidation with Chloramine-T. The latter process appears to be likely to have a wide application in the future, since it can be used for mono- and diarylarsinie acids ... 

The first reported example of the preparation of an arsinimine, in 1937, utilized the reaction of the sodium salt of chloramine T with triphenylarsine (equation 41). This reaction, which has been repeated by later workers is not straightforward. Earlier work had shown that chloramine T reacts with the arsine to convert it into an arsine oxide S which then condenses with the tosylamide to provide the final product. Other arsinimines have been made by the same method, but in the majority of cases were isolated as their water adducts In a modification of this reaction, chloramine T itself, rather than a salt, underwent an exothermic reaction with triphenylarsine in dry benzene, and the resultant intermediate, which was not isolated, gave, on treatment with copper powder, an arsinimine (equation 42) . Other arsinimes have also been made by reactions of chloramines with arsines... 

Drinking water has been disinfected with chlorine for approximately 100 years to protect against waterborne infectious diseases. In addition to chlorination, other methods of drinking water disinfection include the use of chlorine dioxide (either alone or in combination with chlorine), the addition of ammonia to chlorine to form chloramines, ozone treatment, oxidation with potassium permanganate, and ultraviolet radiation. Chlorination, however, is by far the most widely used method. Treatment with chlorine has virtually eliminated cholera, typhoid, dysentery, hepatitis A, and other waterborne diseases)54 ... 

---