Bromide ion effect

For a long time, it was considered that the formation of a bromonium ion from olefin and bromine is irreversible, i.e. the product-forming step, a cation-anion reaction, is very fast compared with the preceding ionization step. There was no means of checking this assumption since the usual methods—kinetic effects of salts with common and non-common ions—used in reversible carbocation-forming heterolysis (Raber et al., 1974) could not be applied in bromination, where the presence of bromide ions leads to a reacting species, the electrophilic tribromide ion. Unusual bromide ion effects in the bromination of tri-t-butylethylene (Dubois and Loizos, 1972) and a-acetoxycholestene (Calvet et al, 1983) have been interpreted in terms of return, but cannot be considered as conclusive. 

Bromide ion acts as an inliibitor through step (9) which competes for HBr02 with the rate detennining step for the autocatalytic process described previously, step (4) and step (5). Step (8) and Step (9) constitute a pseudo-first-order removal of Br with HBr02 maintained in a low steady-state concentration. Only once [Br ] < [Br ] = /fo[Br07]//r2 does step (3) become effective, initiating the autocatalytic growth and oxidation. 

Some reactions require the bonds being broken or made in a reaction to be aligned with other parts ti- or free electrons) of a molecule. These requirements are called stereoelectronic effects. Figure 3-6f shows that the bromide ion has to open a bro-monium ion by an anti attack in order that the new bond is formed concomitantly with the breaking of one bond of the three-membered ring. 

These substances accelerate the reaction, and their effectiveness increases in the order given. This suggestion was questioned by Pocker, who found that the effects of such added substances were not directly proportional to their concentrations and could easily be explained by macro effects on the solvent character. He also found that common-ion effects were small in the reaction, the effect of added 1-methylpyridinium bromide was negligible, and that there was no evidence for surface catalysis on the walls of the vessel. There is an exact parallel between the relative rates of the Finkelstein reactions... 

The ortho indirect deactivating effect of the two methyl groups in 2,6-dimethyl-4-nitropyridine 1-oxide (163) necessitates a much higher temperature (about 195°, 24 hr) for nucleophilic displacement of the nitro group by chloride (12iV HCl) or bromide ions N HBr) than is required for the same reaction with 4-nitropyridine 1-oxide (110°). With 5-, 6-, or 8-methyl-4-chloroquinolines, Badey observed 2-7-fold decreases in the rate of piperidino-dechlorination relative to that of the des-methyl parent (cf. Tables VII and XI, pp. 276 and 338, respectively). 

Precipitation of silver bromide will occur when the concentration of the bromide ion in the solution is 2.0 x 103 times the iodide concentration. The separation is therefore not so complete as in the case of chloride and iodide, but can nevertheless be effected with fair accuracy with the aid of adsorption indicators (Section 10.75(c)). 

Variation of the isotope effect with bromide ion concentration has also been observed for the bromination of 4-methoxybenzenesulphonic acid and its ortho dideuterated derivative at 0 °C, the value of kH/kD changing from 1.0 with no Br to 1.31 at 2.0 M Br" 308. 

This mechanism is further proved by the observation that addition of 0.05 m Br to aqueous DMSO results in reduced intensity of the ethane signal. Bromide ion at this concentration does not effectively compete with DMSO for OH (kom-DMso = 7 x 109 m 1s 1, [DMSO] = 0.23m, k0H + Br = 1-1 x 1010m-1s-1) and the effect of Br can be due to its reaction with the cation of DMSO30 34 found also in pure DMSO, (CH3)2SO + is reduced by Br- and consequently cannot react with the spur electrons. 

In aqueous solution, water competes effectively with bromide ions for coordination to Cir+ ions. The hexaaquacopper(II) ion is the predominant species in solution. However, in the presence of a large concentration of bromide ions, the solution becomes deep violet. This violet color is due to the presence of the tetrabromocuprate(Il) ions, which are tetrahedral. This process is reversible, and so the solution becomes light blue again on dilution with water, (a) Write the formulas of the two complex ions of copper(II) that form, (b) Is the change in color from violet to blue on dilution expected Explain your reasoning. 

The chemoselectivity of the other alkenes of Table 1 is more variable. It appears that bulky substituents favour bromide over methanol attack of the bromonium ion, since dibromlde increases from 39 to 70 % on going from methyl to tert-butyl in the monosubstituted series. The same trend is observed in the disubstituted series with a contraction of the chemoselectivity span (37 to 43 % on going from methyl to teH-butyl) for the trans isomers. Since the solvated bromide ion can be viewed as a nucleophile larger than methanol, the influence of steric effects, important in determining the regioselectivity, does not seem very significant as regards the chemoselectivity. This result has been interpreted in terms of a different balance between polar and steric effects of the substituents on these two selectivities. 

Turco and Faroane and Turco have investigated the effect of bromide ions on the Sb(V)-Sb(III) exchange reaction in 3.15 Af HCl media and have found a complex rate law ... 

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