Ether Synthesis Via Alcohols And Acid

by James

in Alcohols, Organic Chemistry 1

Last post I got a little ahead of myself. I was all excited about getting into the reactions of ethers, and forgot that there’s one last method for ether synthesis that we haven’t covered.

It’s actually not that general so you can likely skip ahead. But for the sake of completeness, here it is.

Remember when we said that alcohols often need a “kick in the pants” in order to participate in reactions? That is, we either add acid to protonate them (forming their conjugate acid, which has a better leaving group) or add base to deprotonate them (forming their conjugate base, which is a better nucleophile).

Today’s post is a perfect example. Here’s the summary.

ether 1

Here’s the deal. If we take a simple alcohol – ethanol is a perfect example – and heat it in the presence of strong acid, ethers can form.

How does this work?

Three steps.

First of all, one equivalent of alcohol is protonated to its conjugate acid  – which has the good leaving group, OH2  (water, a weak base).

Next, another equivalent of the alcohol can now perform nucleophilic attack at carbon (SN2), leading to displacement of OH2 (water) and formation of a new C-O bond.  This is an SN2 reaction.

The final step is deprotonation of the product by another equivalent of solvent (or other weak base), resulting in our ether product.

Here’s the summary:

ether 2

Do I Really Need To Know This?

So how important is this process, really?

Industrially, it’s very important process for the synthesis of diethyl ether, which is a commodity chemical and useful solvent for organic chemistry. Ethanol is cheap. Sulfuric acid is cheap. Heat, distill, and Bob’s your uncle.  Over 10 million tons of the stuff annually via this process.

Practically – and I say this to you, undergraduate student of chemistry –  from a synthetic perspective –it’s not a very general synthesis of ethers. First of all, it’s limited to symmetrical ethers,. Secondly, the temperature has to be carefully optimized, because there are lots of side reactions possible. For example the optimal temperature for the formation of diethyl ether is about 130-140 degrees C. Once the temperature gets to 150 degrees and above, elimination starts to compete, leading to the formation of ethylene gas. And this is for primary alcohols, which don’t form carbocations very easily. Once you get into the category of using this process for secondary and tertiary alcohols, carbocations are much easier to form and elimination becomes an even more significant destructive pathway.

You should know what the correct answer for this question is. And be able to draw the mechanism. That’s it.

ether 3

Beyond that,  unless you’re Sigma Aldrich and are planning to make several metric tons of an ether, you can comfortably omit this method of ether synthesis from your synthetic toolbox. The Williamson ether synthesis will do the job just as well, and can also be used to make unsymmetrical ethers to boot.

Okay . Finally, next post we get to write all about the different reactions of ethers. We’ve learned five (5) – count ’em – ways of making ethers, and now that we’re armed with all this knowledge, we’ll go out and talk about all the different things we can do!

Next Post – Cleavage Of Ethers With Acid

P.S. This synthesis of ethers is so practically straightforward that it lends itself to “How-To” videos. Don’t do this unless you know what you’re doing – ether is extremely flammable.

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{ 4 comments… read them below or add one }

Kaina Chen

Perhaps a dumb question : What is the Wilkinson ether synthesis? Is this another name for the williamson ether synthesis?

Reply

James

Oh dear. There’s a Wilkinson’s catalyst but no Wilkinson’s ether synthesis. It should have been Williamson. Fixed. Thanks Kaina!

Reply

raj

Why this reaction isn’t feasible for unsymmetrical ethers?

Reply

James

The problem is that you get mixtures. If you tried to mix methanol and ethanol in acid, hoping for methyl ethyl ether, you’d also end up with dimethyl ether and diethyl ether. Not very efficient.

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