Bromination substitution versus addition

Fig. 1.28. Derivation of the kinetic expression for the chemoselectivity of allylic substitution versus bromine addition in the Br /Br2/cyclohex-ene system. The rate constants are defined as in Figure 1.27.

The pattern you saw for epoxidation with peroxy-acids (more substituted alkenes react faster) is followed by bromination reactions too. The bromonium ion is a reactive intermediate, so the rate-determining step of the brominations is the bromination reaction itself. The chart shows the effect on the rate of reaction with bromine in methanol of increasing the number of alkyl substituents from none (ethylene) to four. Each additional alkene substituent produces an enormous increase in rate. The degree of branching (Me versus n-Bu versus t-Bu) within the substituents has a much smaller, negative effect (probably of steric origin) as does the geometry (E versus Z) and substitution pattern (1.1- S... 

Examples of the solvent-dependent competition between nucleophilic substitution and / -elimination reactions [i.e. SnI versus Ei and Sn2 versus E2) have already been given in Section 5.3.1 [cf. Table 5-7). A nice example of a dichotomic y9-elimination reaction, which can proceed via an Ei or E2 mechanism depending on the solvent used, is shown in Eq. (5-140a) cf. also Eqs. (5-20) and (5-21) in Section 5.3.1. The thermolysis of the potassium salt of racemic 2,3-dibromo-l-phenylpropanoic acid (A), prepared by bromine addition to ( )-cinnamic acid, yields, in polar solvents [e.g. water), apart from carbon dioxide and potassium bromide, the ( )-isomer of l-bromo-2-phenylethene, while in solvents with low or intermediate polarity e.g. butanone) it yields the (Z)-isomer [851]. 

McMillen, D. W., Grutzner, J. B. Radical Bromination of Cyclohexene in CCI4 by Bromine Addition versus Substitution. J. Org. Chem. 1994, 59, 4516 528. 

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