Ch. 12 - Alcohols, Ethers, Epoxides and ThiolsWorksheetSee all chapters
All Chapters
Ch. 1 - A Review of General Chemistry
Ch. 2 - Molecular Representations
Ch. 3 - Acids and Bases
Ch. 4 - Alkanes and Cycloalkanes
Ch. 5 - Chirality
Ch. 6 - Thermodynamics and Kinetics
Ch. 7 - Substitution Reactions
Ch. 8 - Elimination Reactions
Ch. 9 - Alkenes and Alkynes
Ch. 10 - Addition Reactions
Ch. 11 - Radical Reactions
Ch. 12 - Alcohols, Ethers, Epoxides and Thiols
Ch. 13 - Alcohols and Carbonyl Compounds
Ch. 14 - Synthetic Techniques
Ch. 15 - Analytical Techniques: IR, NMR, Mass Spect
Ch. 16 - Conjugated Systems
Ch. 17 - Aromaticity
Ch. 18 - Reactions of Aromatics: EAS and Beyond
Ch. 19 - Aldehydes and Ketones: Nucleophilic Addition
Ch. 20 - Carboxylic Acid Derivatives: NAS
Ch. 21 - Enolate Chemistry: Reactions at the Alpha-Carbon
Ch. 22 - Condensation Chemistry
Ch. 23 - Amines
Ch. 24 - Carbohydrates
Ch. 25 - Phenols
Ch. 26 - Amino Acids, Peptides, and Proteins

Ethers are almost completely unreactive to reactions. They can only undergo one useful reaction – they can break apart in the presence of strong acid. 

Concept #1: How to predict the products of Ether Cleavage. 


Now I'm going to talk about all the different reactions that ethers undergo. It turns out that you guys are in luck because there's only one. Ethers are actually extremely unreactive. They're very stable. What that means is that there's almost nothing you have to know about ethers in terms of their reactivity. They're pretty much almost as unreactive as alkanes. But there is one reaction that they can be forced to do in the presence of a very strong acid and that is cleavage of ethers. Like I said, I was just trying to scare you guys, it's actually not that bad. Just one reaction and that's it.
Ethers are very combustible like alkanes. They have a lot of energy stored in those bonds. But in terms of breaking those bonds heterolytically so that you get a negative and a positive, that's very difficult to do with ethers because they're very strong bonds. The only thing we can do is that we can cleave them in the presence of strong acid. The acid must be super strong. It can only be HI or HBr. What that means is HCl, HF are not strong enough to make an ether cleave.
Let me go ahead and show you guys this mechanism. Let's go ahead and work with HI since it's the strongest one. Basically what happens here is that the ether protonates. What I wind up getting is that my oxygen and my carbon, that's a very strong bond, but what I can do is I can protonate it first. What that's going to wind up giving me is an ether with a formal charge.
Now that I have that formal charge and now that I have such a good nucleophile present, remember, I- is a very strong nucleophile, I can do a backside attack. So now what I can do is I can take this I and I can attack the carbon chain and I can kick out the OH as a leaving group. What that's going to give me is it's going to give me one equivalent of an alkyl iodide. So I'm going to wind up getting ethyl iodide. And then I'm also going to get ethanol. Because I wind up getting the OH turns neutral again. So I wind up getting this plus this. Cool, right?
But it doesn't end there. Because now that I have the alkyl iodide, that's done. The alkyl halide is done reacting. But the alcohol can actually react again because what I can do now is I can take my alcohol and I can protonate it with another equivalent of HI. What I'm going to do is this and that. And what that's going to give me is that's going to give me OH, H, positive. And then I have an I-.
Now, guys, if you have already studied the conversion of alcohols to good leaving groups, then this is actually that same exact reaction. All we're doing is we're converting alcohol to a good leaving group using HI. That mechanism should be what? Do you guys know? Since it's a primary alcohol, it should be an SN2 mechanism. I would do a backside attack once again.
What I'm going to wind up getting at the very end is I'm going to get another equivalent of alkyl iodide plus water. What this is going to create at the end is not one, but two equivalents of the same alkyl halide. The answer for this question is that what I should put is two times that. That is my actual answer because I'm splitting up the ether into two different sections. I'm cleaving it and I'm getting alkyl halides as a result.
I hope that made sense. So now what I want you guys to do is predict the whole mechanism for this cyclic ether. Now this is a cyclic ether, but it's not technically an epoxide because remember epoxides are three-membered rings. This is a five-membered ring, so we would just call this a cyclic ether. I want you guys to use HBr to figure out what the end product is going to be. This is going to react twice, just like the other reaction. So try your hardest to get this and then I'll show you guys the way. Go for it. 

Example #1: Predict the product of the following reaction.  

Predict the product for the following reaction and determine if the product is given in the answer options below. If the answer is given, select the answer. Write "none" if the answer is not given.
What compounds would you expect to be formed when the following ether is refluxed with excess comcentrated hydrobromic acid?
What are the expected products from the reaction shown?
DRAW THE MOLECULAR STRUCTURE OF THE FOLLOWING REACTION PRODUCT(S). Major organic product (after workup) from the reaction of trans-3,4-dimethyloxacyclopentane (Lewis/Kekule structure at right below) with excess concentrated HBr.
Which of these ethers is least likely to undergo significant cleavage by hot aqueous H2SO4?
Provide the major organic product(s) of the following.   
Draw the structural formulas for the products of the reaction shown below.
Draw the conjugate base for the following acid. Remember to include charges and non-bonding electrons where necessary CH3NH2
Complete the following reaction.
Draw structural formulas for the products of the reaction shown below. You do not have to consider stereochemistry. Assume equimolar amounts of the reagents. Draw one structure per sketcher. Add additional sketchers using the drop-down menu in the Separate multiple products using the - sign from the drop-down menu.
Predict the product(s) for the following reaction.  
Benzyl ethyl ether reacts with concentrated aqueous HI to form two initial organic products (A and B). Further reaction of product B with HI produces organic product C. Draw the structures of these three products.
Draw structural formulas for the products of the reaction shown below. • You do not have to consider stereochemistry. • Assume equimolar amounts of the reagents. • Draw one structure per sketcher. Add additional sketchers using the drop-down menu in the bottom right corner. • Separate multiple products using the + sign from the drop-down menu.
Which one of the following statements about Reaction 4 is correct? a. The major organic product(s) arise via the SN1 pathway b. The major organic product(s) arise via the SN2 pathway