EAS Synthesis Multi Step

Question

In no more than 4 steps, provide the reagents and intermediates for the synthesis of m-hydroxy toluene from toluene as the starting material.

Answer 1

Starting with toluene, we can halogenate with Br₂/FeBr₃ which will yield a mixture of o-and p-bromotoluene. Discarding in the next step the ortho product, we can use NAS to replace the bromine with NH2 by using the reagents NaNH₂/NH₃, which will give us a mixture of p- and m-aminotoluene (or p- and m-methylanaline, which is probably more correct). Again, discarding the para product, we can transform the amino group to the adize ion, which will allow for easy substitution of N2 for OH, by using the reagents NaNO₂/HCl. Once we have our azide ion in the meta position, we simply need to just add H₂O, which will easily substitute for the ⁺N₂, and we have our m-hydroxytoluene product (or you could say m-methylphenol, 3-methylphenol, etc.).