Chloramine, with

Water chlorination is carried out by using both free and combined residuals. The latter involves chlorine application to produce chloramine with natural or added ammonia. Anhydrous ammonia is used if insufficient natural ammonia is present in the wastewater. Although the combined residual is less effective than free chlorine as a disinfectant, its most common application is as a post-treatment following free residual chlorination to provide initial disinfection. 

Reactions of potassium superoxide solubilized in apolar solvents with crown ethers (see Oxidation reactions, p. 356) are also frequently accompanied by elimination reactions. Thus, in DMSO solution, secondary alkyl bromides only yield olefins when treated with the K02 complex of dicyclohexyl-18-crown-6 (Johnson et al., 1978). Scully and Davis (1978) have studied the elimination of HC1 from N-chloramines with 18-crown-6-solubilized K02, KOH, and KOAc in ether solution (27). High yields of aldimines were obtained with K02,... 

N-Chlorocyclohexylideneimine has been prepared by the treatment of N,N-dichlorocyclohexylamine with triethylamine, potassium hydroxide, or potassium acetate and by reaction of chloramine with cyclohexanone or N-cyclohexylideneaniline. ... 

Nitramines have been prepared from the reaction of Ai-chloramines with dinitrogen tetroxide. ... 

Wright et al. [40] elaborated a new method of preparing nitramines by acting on chloramines with nitric acid in the presence of acetic anhydride. A typical example is the preparation of sec-butylnitramine (III) (Smart and Wright Suggitt, Myers and Wright [40]) from dichloramine (I) ... 

Hawkins CL, Pattison DI, Davies MJ (2002) Reaction of Protein Chloramines with DNA and Nucleosides Evidence for the Formation of Radicals, Protein-DNA Cross-Links and DNA Fragmentation. Biochem J 365 605... 

It is worth noting that the adduct of CI3N with BCI3 can be obtained only at low temperature 60>. Hexachloroborazine reacts with water to boric acid and chloramine with methanol, trimethoxyborane and methyl-hypochlorite are produced and, with ethanol, triethoxyborane and acetaldehyde are obtained 59>. Substitution reactions on the B—N ring of hexachloroborazine have not yet been studied. 

The Bayer Ketazine process is based on the reaction of chloramine with ammonia in the presence of acetone at pH 12 to 14. NaOCl, acetone and a 20% aqueous solution of ammonia (at a mole ratio of 1 2 20, respectively) are fed to a reactor at 35°C and 200 kPa to make the aqueous dimethyl ketazine solution. Excess ammonia and acetone are removed in a series of columns and recycled to the reactor. The ketazine solution is distilled to make a hydrazine hydrate containing 64% hydrazine. A sketch of this process is shown in Figure 18.4132. Use of NaOCl is estimated to be 3.5 pounds per pound of hydrazine. 

The reaction of trialkylboranes with iV-chloroalkylamines can be used to synthesize a wide variety of functionally substituted dialkylamines in good yields [66,67], and it complements the synthesis of secondary amines via the reaction of trialkylboranes with organic azides. The reaction is analogous to the reaction of chloramine with organoboranes, and presumably occurs via an anionotropic migration of an alkyl group from boron to nitrogen (Scheme 24). 

Diimine is prepared by the reaction of chloramine with a base ... 

In anhydrous systems, the low hydrazine concentration is avoided. Chlorine and ammonia can react in the gas phase to form chloramine, which then reacts with ammonia to form hydrazine. As in the Raschig process, the reaction (57) of chloramine with hydrazine limits the yields. Substituted hydrazines can be prepared using this process with the appropriate substituted amines. 

The Raschig hydrazine synthesis can be extended one further step. Reaction of chloramine with hydrazine in ether yields triazanium chloride, which decomposes instantaneously. This is responsible for hydrazine decomposition during the Raschig synthesis (see Section 5.2.1) ... 

The reaction of chloramine with A,A-disnbstitnted hydrazines R2NNH2 yields stable triazaninm salts ... 

Simple primary alkylamines can be converted into the corresponding monoaUcylhydrazines in moderate yield by amination with chloramine or with hydroxylamine-O-sulfonic acid. The method is tolerant of Ae presence of double bonds allylhydrazine was prepared (52%) by reaction of chloramine with allylamine. The method is not generally tqjplicable to the preparation of 1,2-disubstimted hydrazines from primary alkylamines and N-chloroalkylamines although intramolecular examples are known. Te-trahy opyrazole was prepared in moderate yield in this way (Scheme 12) and piperazine was prepared in low yield by the same type of reaction. 

A bromine-initiated method for the preparation of sulfonate-linked aziridines has been developed <2001TL1037>. Treatment of the sulfonamide with r-butylhypochlorite generates the intermediate Wchloramine salt. Reaction of the chloramine with phenyltrimethylammonium bromide (PTAB) provides the sulfonamide-linked aziridine. This method does not provide any improvement in yield relative to either the copper- or rhodium-catalyzed reaction systems. It does however work for the preparation of the bicyclo[5.1.0] system as both the copper- and rhodium-catalyzed reactions give C-H insertion products in this attempt to prepare the larger ring system (entry 6). 

The reaction of chloramine with hydroxide ion has been discussed in Section 4.8.2 (p.311). 

Dicyonamide (called Dicyanamid, Dicyanimid or Imino-dicarbonsaure-dinitril in Get), NC.NH.CN mw 67.05, N 62.67% ndls + H2O obtd by reacting chloramine with an aq soln of KCN and by other methods forms some unstable salts such as ... 

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... 

The reactants are mixed at a low temperature and rapidly heated to promote reaction of the chloramine with ammonia. Glue or gelatine is used to inhibit the secondary reaction ... 

Because ozone is employed only for primary disinfection, a chlorinated compound (chlorine or chloramine) must be added for secondary disinfection following ozonation, i.e., to provide a residual for the distribution system. Consequently, the secondary byproducts, those formed by the reaction of chlorine or chloramine with the primary byproducts of ozonation, become a concern to water treatment specialists. Although some studies have examined by-products produced by two-step oxidation sequences of this type, no compounds have yet been reported that are not produced by one of the two oxidation processes acting alone. 

For most uses, hydrazine is produced as hydrazine hydrate in a formulation with water. The hydrate may be produced commercially by three methods the Raschig process, the ketazine process, and the peroxide process. The Raschig process, the original commercial production process for hydrazine, involves oxidation of ammonia to chloramine with sodium hypochlorite, then further reaction of the chloramine with excess ammonia and sodium hydroxide to produce an aqueous solution of hydrazine with sodium chloride as a by-product. Fractional distillation of the product yields hydrazine hydrate solutions. Currently, most hydrazine is produced by the ketazine process, which is a variation of the Raschig process. Ammonia is oxidized by chlorine or chloramine in the presence of an aliphatic ketone, usually acetone. The resulting ketazine is then hydrolyzed to hydrazine. In the peroxide process, hydrogen peroxide is used to oxidize ammonia in the presence of a ketone. Anhydrous hydrazine is the formulation used in rocket fuels and is produced by dehydration of the hydrate by azeotropic distillation with aniline as an auxiliary fluid (Budavari et al. 1989 lARC 1974 Schmidt 1988 WHO 1987). 

Diazo-A-norcholestan-l-one (114) is prepared from 5y -2-oximino-A-norcholestan-l-one (113) with chloramine in aqueous ether in 63% overall yield.20,43"45 Steroidal ketones 115 and 118 (D-ring and A-ring) are converted to the corresponding diazoketones 117 and 120 via ketoximes 116 and 119 using chloramine with w-butyl nitrite and /-BuOK in 55% and 78% yields, respectively.46... 

Reaction of N-chloramines with aromatics [(153)-(155)] has been illustrated most recently with alkylaromatics by Clerici et al. (1974). Amination of aromatics is an electrophilic rather than free-radical... 

Hypochlorous acid reacts with ammonia to give the less active substance, chloramine (NH2CI), which is often used where a depot effect is required, e.g. in swimming pools. Similarly, hypochlorous acid forms substituted chloramines with amino acids and proteins, both outside and inside the cell. These can also act as depots, because they are in equilibrium with hypochlorous acid. Finally an artificial chloramine, / -toluenesulfonylchloramide (Chloramine-T) is used by campers as a source of hypochlorous acid. 

Urea and related compounds were separated by HPLC, and the peaks emerging from the column were converted to the N-chloramines with hypochlorite. Excess reagent... 

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