Forming Hemiacetals with Acid???

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justadream

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TBR says hemiacetals can only be formed with bases (using acid would form an acetal and you can't stop the reaction at hemiacetal).

However, my textbook (Wade 8th edition) - see the two pictures - shows a hemiacetal being formed with acids.
 

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TBR says hemiacetals can only be formed with bases (using acid would form an acetal and you can't stop the reaction at hemiacetal).

However, my textbook (Wade 8th edition) - see the two pictures - shows a hemiacetal being formed with acids.
A hemiacetal does form briefly in acid catalyzed reactions (it's an intermediate), but like TBR explained, it's not something you can isolate because the forward reaction is very favorable. By the end of the reaction, you'll end up with a solution composed predominately of acetals. With base on the other hand, only hemiacetals can be formed. -OH is not a good leaving group. It would need to leave in order for another alkoxide ion to come in and attack to form an acetal. Just won't happen for base catalyzed reactions. With acid catalyzed reactions, after hemiacetal formation, the -OH is first protonated, forming a good leaving group (H2O). This allows another alcohol to come in and displace water to form the acetal (very favorable).
 
Right, I understand that hemiacetals are formed under acidic conditions (as part of the process of making acetals).

So if a question asks whether acidic conditions can be used to make hemiacetals, should the answer be "no" because it's not possible to isolate it?
 
Right, I understand that hemiacetals are formed under acidic conditions (as part of the process of making acetals).

So if a question asks whether acidic conditions can be used to make hemiacetals, should the answer be "no" because it's not possible to isolate it?
If they are asking for the major product, which is typically the question they'll ask, then the answer is no, because in this case, the major product (in acid catalyzed rxn) would be an acetal. However, if instead they asked what intermediate is formed, then the answer is hemiacetal. I believe that's the distinction TBR was trying to make, but worded it poorly.
 

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