Halogenated hydrocarbons nucleophilic substitution reactions

Let us now look at some examples to illustrate what we have discussed so far to get a feeling of how structural moieties influence the mechanisms, and to see some rates of nucleophilic substitution reactions of halogenated hydrocarbons in the environment. Table 13.6 summarizes the (neutral) hydrolysis half-lives of various mono-halogenated compounds at 25°C. We can see that, as anticipated, for a given type of compound, the carbon-bromine and carbon-iodine bonds hydrolyze fastest, about 1-2 orders of magnitude faster than the carbon-chlorine bond. Furthermore, we note that for the compounds of interest to us, SN1 or SN2 hydrolysis of carbon-fluorine bonds is likely to be too slow to be of great environmental significance. 

Many halogenated hydrocarbons are substrates for GSH-transferase-catalyzed nucleophilic substitution reactions that produce S-substituted glutathione (GSH) derivatives. These are normal SN2 displacements of halide with thiolate anion that occur with inver-... 

Classes of organic pollutants that hydrolyze via nucleophilic substitution reactions include the halogenated hydrocarbons, epoxides, and phosphorus esters. Further discussion of the factors affecting the reactivity of nucleophilic substitution reactions will be made as the hydrolysis mechanisms of these chemicals are examined in greater detail. 

The apparent rate of hydrolysis and the relative abundance of reaction products is often a function of pH because alternative reaction pathways are preferred at different pH. In the case of halogenated hydrocarbons, base-catalyzed hydrolysis will result in elimination reactions while neutral hydrolysis will take place via nucleophilic displacement reactions. An example of the pH dependence of hydrolysis is illustrated by the base-catalyzed hydrolysis of the structurally similar insecticides DDT and methoxy-chlor. Under a common range of natural pH (5 to 8) the hydrolysis rate of methoxychlor is invariant while the hydrolysis of DDT is about 15-fold faster at pH 8 compared to pH 5. Only at higher pH (>8) does the hydrolysis rate of methoxychlor increase. In addition the major product of DDT hydrolysis throughout this pH range is the same (DDE), while the methoxychlor hydrolysis product shifts from the alcohol at pH 5-8 (nucleophilic substitution) to the dehydrochlorinated DMDE at pH > 8 (elimination). This illustrates the necessity to conduct detailed mechanistic experiments as a function of pH for hydrolytic reactions. 

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