Solomons and Fryhle has an example in which they have showed a very simple substitution reaction. The question was to synthesize methyl iodide. What they have done is taken methyl chloride and produced methyl iodide in the presence of $\ce{NaI}$ and ethanol through an $\mathrm{S_N2}$ mechanism.
Why did they use ethanol? I have read that $\mathrm{S_N2}$ reactions are favored under polar aprotic solvents and clearly ethanol is not that. Also, since it's a methyl and all substitution reactions on methyl go through $\mathrm{S_N2}$; so how would it affect my reaction if I would't use ethanol?
Answer
Usually, nucleophilic substitution reactions of anionic nucleophiles occur more rapidly in polar aprotic solvents. In such solvents (e.g. DMSO) the typical relative reactivity order is
$$ \ce{SCN-} < \ce{I-} < \ce{Br-} < \ce{Cl-} < \ce{F-}$$
In protic hydrogen-bonding solvents (e.g. ethanol), anions are solvated. Therefore, the reactivity of nucleophiles is decreased. Since hard nucleophiles are more strongly solvated than soft nucleophiles, the relative reactivity of soft anions is increased in such solvents. The typical relative reactivity order is
$$ \ce{F-} < \ce{Cl-} < \ce{Br-} < \ce{I-} < \ce{SCN-}$$
In the given example, $\ce{-Cl}$ shall be replaced by $\ce{-I}$; and in alcohols, the nucleophilicity of $\ce{I-}$ is higher than the nucleophilicity of $\ce{Cl-}$.
No comments:
Post a Comment