Dichloramine

Dichloramine-T. Dilute 80 ml, of freshly prepared 2N sodium hypochlorite soluticMi (preparation, p. 525) with 80 ml. of w ter, and then add with stirring 5 g. of finely powdered toluene-p-sulphonamide, a clear solution being rapidly obtained. Cool in ice-water, and then add about 50 ml. of a mixture of equal volumes of glacial acetic acid and water slowly with stirring until precipitation is complete the dichloro-amide separates at first as a fine emulsion, which rapidly forms brittle colourless crystals. Filter off the latter at the pump, wash well with... 

Both chloramine-T and dichloramine-T have marked antiseptic properties, chloramine-T being most frequently used because of its solubility in water. Aqueous solutions of chloramine-T can be used either for external application, or for internal application to the mouth, throat, etc, as chloramine-T in moderate quantities is non-toxic its aqueous solution can also be effectively used when the skin has come in contact with many of the vesicant liquid poison-gases, as the latter are frequently organic sulphur or arsenic derivatives which combine with or are oxidised by chloramine-T and are thus rendered harmless. 

Both chloramine-T and dichloramine-T can be readily estimated, because they liberate iodine from potassium iodide quantitatively in the presence of... 

Dichloramine-T and chloramine-T. When p toluenesulphonamide is dissolved in excess of sodium (01 calcium) hypochlorite solution, it is converted into the soluble salt of the N-monochloro derivative ... 

Upon the addition of a weak acid (e.g., acetic acid), it reacts with the liberated hypochlorous acid giving NA -dichloro-p-toluenesulphonamide (dichloramine-T) which, being insoluble in water, crystallises rapidly ... 

When the dichloramine-T is heated with sodium hydroxide solution, the reverse change occurs and sodium N-chloro-p-toluenesulphoiiamide (chloramine-T) crystallises out on cooling at a suitable concentration ... 

Both chloramine-T and dichloramine-T slowly liberate hypochlorous aeid in eontaet with water and are therefore employed as antiseptics the former is employed in the form of a dilute (e.g., 0-2 per eent.) aqueous solution, and the latter (which is insoluble in water) as a solution in an organic solvent, such as a chlorinated paraffin. 

FLUORINECOMPOUNDS, ORGANIC - FLUORINATED AROMATIC COMPOUNDS] (Volll) Pentafluorosulfanyl-N,N-dichloramine [22650-46-0]... 

Monochloramine is oxidized slightly faster than ammonia (40). Monohromamine reacts much faster, k = 4Q (39). By contrast, dichloramine and dibromamine both react slower than m on oh a1 amines their k values are 1.3 and 20, respectively. 

A number of perhalides aie known, and one of the most stable is ammonium tetiachloioiodide [19702 3-3] NH IQ. Ammonia reacts with chlorine in dilute solution to give chloramines, a reaction important in water purification (see Cm,ORAMINES AND BROMAMINEs). Depending upon the pH of the water, either monochloramine [10599-90-3] NH2CI, or dichloramine [3400-09-7] NHCI2, is formed. In the dilutions encountered in waterworks practice, monochloramine is neady always found, except in the case of very acidic water (see Bleaching AGENTS Water). 

In reahty the chemistry of breakpoint chlorination is much more complex and has been modeled by computer (21). Conversion of NH/ to monochloramine is rapid and causes an essentially linear increase in CAC with chlorine dosage. Further addition of chlorine results in formation of unstable dichloramine which decomposes to N2 thereby causing a reduction in CAC (22). At breakpoint, the process is essentially complete, and further addition of chlorine causes an equivalent linear increase in free available chlorine. Small concentrations of combined chlorine remaining beyond breakpoint are due primarily to organic chloramines. Breakpoint occurs slightly above the theoretical C1 N ratio (1.75 vs 1.5) because of competitive oxidation of NH/ to nitrate ion. Organic matter consumes chlorine and its oxidation also increases the breakpoint chlorine demand. Cyanuric acid does not interfere with breakpoint chlorination (23). 

The lack of dependence on ionic strength in the first reaction indicates that it occurs between neutral species. Mono- or dichloramine react much slower than ammonia because of their lower basicities. The reaction is faster with CI2 because it is a stronger electrophile than with HOCl The degree of chlorination increases with decreasing pH and increasing HOCINH mol ratio. Since chlorination rates exceed hydrolysis rates, initial product distribution is deterrnined by formation kinetics. The chloramines hydrolyze very slowly and only to a slight extent and are an example of CAC. 

Some nitrate is also formed, thus the HOCl/NH stoichiometry is greater than theoretical, ie, - 1.7. This reaction, commonly called breakpoint chlorination, involves intermediate formation of unstable dichloramine and has been modeled kinetically (28). Hypobromous acid also oxidizes ammonia via the breakpoint reaction (29). The reaction is virtually quantitative in the presence of excess HOBr. In the case of chlorine, Htde or no decomposition of NH occurs until essentially complete conversion to monochloramine. In contrast, oxidation of NH commences immediately with HOBr because equihbrium concentrations of NH2Br and NHBr2 are formed initially. As a result, the typical hump in the breakpoint curve is much lower than in the case of chlorine. 

Dichloramine. The least stable chloramine, dichloramine [3400-09-7] has not been prepared in pure form. However, it has sufficient stabiUty in dilute organic or aqueous solutions for deterrnination of some physical and chemical properties. It has a pungent odor and can impart an odor or off-taste to water at concentrations above 0.8 ppm. Dichloramine can be produced by reaction of HOCl with a slight excess of NH in the pH range 4—7 or by disproportionation of NH2CI at pH 3.5—4.0 ... 

Prepared by the latter route, decomposition is - 10% in 24 h. This reaction involves direct Cl transfer to NH2CI via the intermediate NH CE NH2CI hydrolysis playing Htde or no role. The presence of NH" 4 improves stabiUty by reacting with HOCl which tends to increase decomposition (39). Trichloramine also increases decomposition, whereas NH2CI has Httle effect. Dichloramine is useful for preparation of diazirine (40). 

Hypochlorous acid reacts very rapidly and quantitatively with a slight excess of free ammonia forming monochloramine, NH2CI, which reacts at a slower rate with additional HOCl forming dichloramine, NHCI2. Trichloramine is formed when three moles of HOCl are added per mole of ammonia between pH 3—4 (100). Hypochlorous acid in the form of chlorine or hypochlorite is used in water treatments to oxidize ammonia by the process of break-point chlorination, which is based on formation of unstable dichloramine. The instabiHty of NHCI2 is caused by presence of HOCl and NCl (101,102). The reaction is most rapid at a pH of about 7.5 (103). Other nitrogen compounds such as urea, creatinine, and amino acids are also oxidized by hypochlorous acid, but at slower rates. Unstable iV-chloro compounds are intermediates in deammination of amino acids (104,105). 

Dichloramine-T, A/ W-dichloro-T -toluenesulfonamide [473-34-7] is insoluble in water, but soluble in a number of organic solvents, including chlorinated paraffin. Its medical usage appears to have declined. 

The parent compound, cyclic diazomethane , was first obtained from formaldehyde, ammonia and chloramine by dichromate oxidation of the initially formed higher molecular diaziridine-formaldehyde condensation product (61TL612). Further syntheses of (44) started from Schiff bases of formaldehyde, which were treated with either difluoramine or dichloramine to give (44) in a one-pot procedure. Dealkylation of nitrogen in the transient diaziridine was involved (65JOC2108). 

Phenyl dichloramine (N, N-Dichlo raniline). C6H5.NCI2, mw 162.02, yel-red oil. It was prepd by Goldschmidt (Ref 2) by action of hypochlorous acid on aniline in ethereal soln at —15° to 20°. Sol in eth the soln is fairly stable when kept at 0° and in the dark. The oil alone is stable at - 10°, but explds at higher temps. It also explds on contact with coned sulfuric acid... 

Acidification of chloramine T with sulfuric acid produces the formation of dichloramine T (DCT) and hypochlorous acid (HCIO), species which react with C=C bonds of the butadiene units. The effectiveness of the treatment is ascribed to the introduction of chlorine and oxygen moieties on the mbber surface. A decrease in the pH of the chloramine T aqueous solutions produced more extended surface modifications and improved adhesion properties in the joints produced with waterborne polyurethane adhesive (Figure 27.9). The adhesive strength obtained is slightly lower than that obtained for the rubber treated with 3 wt% TCI/MEK, and its increases as the pH of the chloramine T solution decreases (Figure 27.9). A cohesive failure in the rubber is generally obtained. 

A number of organic chlorine, or chloramine, compounds are now available for disinfection and antisepsis. These are the N-chloro (=N-C1) derivatives of, for example, sulphonamides giving compounds such as chloramine-T and dichloramine-T and halazone (Fig. 10.5), which may be used for the disinfection of contaminated drinking water. 

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