WikiPremed Question

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MedPR

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I'm looking at acid catalyzed hydration of alkenes on wikipremed and I'm confused by the oxonium ion.

http://www.wikipremed.com/03_organicmechanisms.php?mch_code=030202_020

Shouldn't there be only 1 lone pair on that oxygen, thus giving it only 5 electrons (8 shared) and the positive charge? The way it's drawn currently shows that it has a total of 10 shared electrons.

Yes, it does appear he failed to drop a LP in the step that formed the oxonium ion. It carries over into his final product which also has 10 electrons on the O 😱
 
Alright, thanks for the replies. I'm glad I wasn't completely mistaken on that.
 
Sorry for the error.

It's fixed now.

I really hate to be the bearer of bad news but it appears you over-deleted.

The oxonium should have 1-LP, and the alcohol 2.

You had 2/3 but now there are 0 LP in either structure 🙁

Otherwise, I agree the rapid response was great.
 
I really hate to be the bearer of bad news but it appears you over-deleted.

The oxonium should have 1-LP, and the alcohol 2.

You had 2/3 but now there are 0 LP in either structure 🙁

Otherwise, I agree the rapid response was great.

Good catch. I didn't even check to see if it had been correctly fixed 🙄
 
I really hate to be the bearer of bad news but it appears you over-deleted.

The oxonium should have 1-LP, and the alcohol 2.

You had 2/3 but now there are 0 LP in either structure 🙁

Otherwise, I agree the rapid response was great.

I understand why comparison to the original mistaken drawing would lead to that conclusion. I'm sorry about the original mistake because those kinds of things waste your time, but I think the new version is okay. In making the change, I decided not only to remove the extra pairs but to go all the way to applying the normal textbook convention, which is to show the lone pairs on oxygen only at the stage that a pair is participating nucleophilically, but otherwise, to leave them off of the structural formulas. For example, showing the bonds but not the lone pairs is how we typically draw a hydroxyl group, and I think any person looking at them with fresh eyes would understand them correctly as they are now. So, how it is now is how it is generally done, how I should have done it originally.

And thank you MedPR for pointing out the 'alkene' mistakenly labeled as an 'alkyne'. I think if you made it a mission, you would have a hard time finding another mistake! I probably shouldn't say that. Good editing is something I take really seriously, but this goes to show how difficult the challenge can be. These mechanisms have had the fine tooth comb over them many times, so still to find a drag and paste artifact, let alone two, after all these years, really does upset me, though I really am glad you pointed them out. I'm really grateful when folks point out these things because it helps me make WikiPremed better.

Actually, the second one really sticks in my craw, the 'alkyne' 'alkene' error (which I will fix tomorrow), though the proper label really isn't 'alkene', but actually 'enol'. I can't tell you how many times I have sat with students looking at that mechanism and used it to foreshadow the major topic of keto-enol tautomerism in my teaching. All of us seeing and not seeing 'alkyne' there plain as day.

Anyway, good luck in your studies! All the best.
 
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I understand why comparison to the original mistaken drawing would lead to that conclusion. I'm sorry about the original mistake because those kinds of things waste your time, but I think the new version is okay. In making the change, I decided not only to remove the extra pairs but to go all the way to applying the normal textbook convention, which is to show the lone pairs on oxygen only at the stage that a pair is participating nucleophilically, but otherwise, to leave them off of the structural formulas. For example, showing the bonds but not the lone pairs is how we typically draw a hydroxyl group, and I think any person looking at them with fresh eyes would understand them correctly as they are now. So, how it is now is how it is generally done, how I should have done it originally.

And thank you MedPR for pointing out the 'alkene' mistakenly labeled as an 'alkyne'. I think if you made it a mission, you would have a hard time finding another mistake! I probably shouldn't say that. Good editing is something I take really seriously, but this goes to show how difficult the challenge can be. These mechanisms have had the fine tooth comb over them many times, so still to find a drag and paste artifact, let alone two, after all these years, really does upset me, though I really am glad you pointed them out. I'm really grateful when folks point out these things because it helps me make WikiPremed better.

Actually, the second one really sticks in my craw, the 'alkyne' 'alkene' error (which I will fix tomorrow), though the proper label really isn't 'alkene', but actually 'enol'. I can't tell you how many times I have sat with students looking at that mechanism and used it to foreshadow the major topic of keto-enol tautomerism in my teaching. All of us seeing and not seeing 'alkyne' there plain as day.

Anyway, good luck in your studies! All the best.

Haha, I'm not trying to find errors I promise. I'm studying for my retake and am going to spend a lot more attention to detail this time around. I'll post anything else I find in this thread and hopefully you'll get a chance to see it!

Edit: Plus, those two errors were very minor. Everyone knows how many lone pairs should be on an Oxygen, and everyone knows a double bond =/= an alkyne.
 
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When I learned oxymercuration-demercuration, there was no carbocation intermediate (hence no rearrangement). The intermediate is a mercurinium ion, which is a 3 membered ring formed by the two formerly double bonded carbons and Hg+ from one of the Hg(OAc) ions -- R-C-HgOAc-C-R.

The way it's drawn here: http://www.wikipremed.com/03_organicmechanisms.php?mch_code=030202_110
doesn't really prevent rearrangement, which kind of defeats the purpose of this reaction since it exists in part to produce greater purity than an acid-catalyzed hydration reaction.
 
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