Monday, 5 December 2016

organic chemistry - Reduction of carboxylic acids by LiAlH4


I've read that when a carboxylic acid reacts with $\ce{LiAlH4}$ the corresponding alcohol is formed:


enter image description here



But when I try to think of the mechanism, I get stuck here:


$\ce{LiAlH4}$ produces $\ce{H-}$. Since $\ce{H-}$ is a strong base it should immediately abstract a proton from the carboxylic acid to give the corresponding carboxylate ion (just like in the reaction of carboxylic acids with Grignard reagents), instead of undergoing nucleophilic addition to give the alcohol.


How do I resolve this?



Answer



The $\ce{Li^+}$ ion substitutes the $\ce{OH}$ in $\ce{COOH}$ first. The $\ce{C=O}$ is then reduced by $\ce{AlH_3}$ to give an aldehyde. See below:


enter image description here


Another $\ce{LiAlH_4}$ then reduces the aldehyde to alcohol: enter image description here


I found the pictures here.


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