Hypobromous acid, reaction with

Christen and Zollinger303 have made an extensive study of kinetic isotope effects in bromination of the disodium salt of 2-naphthol-6,8-disulphonic acid with hypobromous acid and with bromine in aqueous buffers at 20 °C. Both bro-minating agents give the same rate (within 20 %) and the reactions are first-order... 

Reactions with ammonia and organic compounds. Hypobromous acid reacts with amines to form bromamines in a manner similar to ehorine. However bromamines are efficacious as sanitizers in recreational water, unlike chloramines which are biocidal, but of limited value due to their slow rate of kill. Additionally, bromamines are not irritating to the skin and eyes and do not possess a strong odor. Breakpoint bromination is not required. Re-oxidation of the inactive bromide ions will re-convert the salt to biocidal form (HOBr/OBr ). These qualities make bromine biocides much more favorable products for use in spas, relative to chlorine. Bromine products are primarily used for treating indoor pools and spas. Chemicals used for the neutralization of hypobromous acid are identieal to those used for hypochlorous acid. 

In the olivanic acid series of carbapenems the ( )-acetamidoethenyl grouping can be isomerised to the (Z)-isomer (19) (22) and reaction with hypobromous acid provides a bromohydrin that fragments to give a thiol of type (20) when R = H, SO H, or COCH. The thiol is not isolated but can react to provide new alkyl or alkenyl C-2 substituents (28). In the case of the nonsulfated olivanic acids, inversion of the stereochemistry at the 8(3)-hydroxyl group by way of a Mitsunobu reaction affords an entry to the 8(R)-thienamycin series (29). An alternative method for introducing new sulfur substituents makes use of a displacement reaction of a carbapenem (3)-oxide with a thiol (30). Microbial deacylation of the acylamino group in PS-5 (5) has... 

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. 

Addition to the Double Bond. Chlorine, bromine, and iodine react with aHyl chloride at temperatures below the inception of the substitution reaction to produce the 1,2,3-trihaLides. High temperature halogenation by a free-radical mechanism leads to unsaturated dihalides CH2=CHCHC1X. Hypochlorous and hypobromous acids add to form glycerol dihalohydrins, principally the 2,3-dihalo isomer. Dehydrohalogenation with alkah to epicbl orobydrin [106-89-8] is ofgreat industrial importance. 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Bromination with A-bromosuccinimide generally gives the same result as bromination with free bromine or hypobromous acid. The reaction is considered to proceed with a small concentration of free bromine and does not generate an appreciable concentration of acid. Conditions are therefore mild. In addition, A-bromosuccinimide has been used to brominate the allylic position of a, -unsaturated ketones in the presence of free-radical promoters or with irradiation, and thus gives access to dienones by dehydro-halogenation, for exaraple " ... 

Derbyshire and Waters192 measured the rates of bromination of sodium toluene-m-sulphonate (in water) and of benzoic acid (in aqueous acetic acid) by hypobromous acid with sulphuric or perchloric acids as catalysts, all at 21.5 °C. No bromination occurred in the absence of mineral acid and the reaction was strictly first-order in aromatic and in hypobromous acid. The function of the catalyst was considered to be the formation of a positive brominating species, according to the equilibrium... 

The positive bromination of aromatics ethers was first studied by Bradfield et al.193 and by Branch and Jones194. The reaction of hypobromous acid in 75 % aqueous acetic acid with benzyl 4-nitrophenyl ether and 4-nitrophenetole at 20 °C was very rapid and approximately second-order193. The value of k2/[H+] remained constant in the [H+] range 0.005-0.090 M for the effect of added mineral acids on the bromination of 4-nitroanisole and 4-nitrophenetole (at 19.8 °C)194. The variation in reaction rate with the percentage of acetic acid in the medium was also studied and showed a large increase in the 0-10 % range with a levelling off at approximately 25 % acetic acid (Table 52) this was attributed... 

At 0.9 °C the rate of bromination of biphenyl relative to benzene was approximately 1,270, compared to 26.9 in the presence of mineral acid, and this latter value is fairly close to that obtained with 50 % aqueous dioxan. The possibility that the positive brominating species might be protonated bromine acetate, AcOHBr+, was considered a likely one since the reaction rate is faster in aqueous acetic acid than in water, but this latter effect might be an environmental one since bromination by acidified hypobromous acid is slower in 50 % aqueous dioxan than in... 

Kinetic studies using acidified hypochlorous acid are rather more complicated than these with hypobromous acid. Much higher concentrations of mineral acid are necessary so that the activities of the reacting entities do not correspond closely to their molecular concentrations, and the kinetic order of reaction varies according to the acid concentration and the reactivity of the aromatic. 

Not only were the reaction rates for bromination by bromine and by hypobromous acid very similar, but the corresponding activation energies (determined over a 20 °C range) were between 11.8 and 12.6 (for Br2) and 12.5 and 12.7 (for HOBr). Thus all this kinetic data is consistent with the rapid formation of an intermediate which is identical for both brominating reagents, and from which the slow loss of a proton subsequently occurs. 

Bromine sulphate BrHS04 has been proposed as a possible molecular bro-minating species, since the catalysis by sulphuric acid of the bromination of benzoic acid by hypobromous acid was much greater than by perchloric acid of the same acidity198. Its reactivity was considerably less than that of H2OBr+ so that an enhanced rate spread is observed and its reactions only become noticeable with the least deactivated (i.e. most reactive) compounds employed in this particular study. 

Whilst molecular hypobromous acid can be a brominating species, it is not believed to be the active species in acetic acid solution. The bromination of 4-nitroanisole by hypobromous acid in 75 % aqueous acetic acid at 19.8 °C gave a second-order rate coefficient of 0.162, so that the brominating species here appears to be more reactive than molecular bromine194. In addition, the presence of 0.05 M sodium acetate caused the rate coefficient to fall to only 0.040, and both these observations were contrary to expectation if hypobromous acid was the brominating species, but are quite consistent with it being bromine acetate, BrOAc. Also, the addition of chloride ion caused the reaction to become immeasurably slow, due to the formation of the much less reactive bromine chloride. 

The hydroxyl in (42-6) is then acylated with p-toluenesulfonyl chloride exposure of this to a base leads to elimination to form the 9,11 olehn (43-1). It should be noted that the hydroxyl group in the hrst-obtained fermentation product is equatorial and would eliminate only with great difficulty as it lacks a transoid proton at the adjacent position. Reaction of (43-1) with A -bromosuccinimide in an aqueous base leads to the addition of the elements of hypobromous acid. The stereochemistry of the reaction... 

The acid is formed in many reactions with hypobromous acid for example, when... 

Chlorine, bromine, hypoehlorous acid and hypobromous acid also convert thiosulphate into tetrathionate, but their activity is so great that the reaction tends to proceed still further, with formation of sulphate.2... 

---