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Topic: How to close a ring with only sulfuric acid?  (Read 7363 times)

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Offline jagg

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How to close a ring with only sulfuric acid?
« on: March 01, 2012, 07:27:19 PM »
Here is the reaction: http://i.imgur.com/vo8lF.png

Attempt at mechanism:

i.) H2SO4 reacts at the alkene via Markovnikov addition. The --O-SO2-OH adds at the terminal carbon because it has more substituents.

OR

ii.) H2SO4 in equilibrium produces SO3 (is it wrong to assume sulfonation is possible when the only reagent provided is H2SO4?). Alkyl groups are ortho/para directors. Sulfonation of the aromatic ring occurs at the ortho position. The pi bond at the alkene bonds with the ortho carbon and the sulfur group is a leaving group.

Problems

i.) Not sure how to close the ring from here

ii.) This leaves a carbocation on the ring, and I'm not sure how to resolve this. It makes me suspect the mechanism would not occur this way.

Offline g-bones

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Re: How to close a ring with only sulfuric acid?
« Reply #1 on: March 01, 2012, 07:47:59 PM »
It may be worth looking into the mechanism of the Friedel Crafts alkylation.  How do olefins react with strong acids?  These two are connected  :P

Offline Enthalpy

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Re: How to close a ring with only sulfuric acid?
« Reply #2 on: March 02, 2012, 10:16:56 AM »
Would the proton really go to the tertiary carbon at the double bond?
I imagine carbons at the aromatic ring are stronger candidates because electrons are shared among more atoms. In fact, each carbon there has 5 immediate neighbours.
Did I read somewhere that Markovnikov's rule agrees with that?

Offline Honclbrif

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Re: How to close a ring with only sulfuric acid?
« Reply #3 on: March 02, 2012, 12:14:44 PM »
You might have had a hiccup in counting your carbons. Protonation of the tertiary site would not lead to the indicated product.
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Offline Doc Oc

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Re: How to close a ring with only sulfuric acid?
« Reply #4 on: March 02, 2012, 01:40:18 PM »
I imagine carbons at the aromatic ring are stronger candidates because electrons are shared among more atoms. In fact, each carbon there has 5 immediate neighbours.

This would disrupt the aromaticity, and that's a deep thermodynamic well.  The alkene would be a much easier target.

Offline opsomath

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Re: How to close a ring with only sulfuric acid?
« Reply #5 on: March 02, 2012, 01:44:35 PM »
The first thing to ask yourself is always "What is the most basic electron pair?" when reacting with an acid, and vice versa with a base.

The alkene is much more basic than the aryl ring. Start by protonating it to form a tertiary carbocation and go from there.

The structure is correct as written.

Offline Honclbrif

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Re: How to close a ring with only sulfuric acid?
« Reply #6 on: March 02, 2012, 02:43:24 PM »
Wait a minute. opsomath?

I haven't seen you around here in forever! Hope everything is ok.
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Offline Enthalpy

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Re: How to close a ring with only sulfuric acid?
« Reply #7 on: March 02, 2012, 06:44:31 PM »
Thanks about the phenyl, I had understood wrongly a book.

Offline opsomath

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Re: How to close a ring with only sulfuric acid?
« Reply #8 on: October 04, 2012, 01:36:34 PM »
Hah, thanks, Honclbrif. I've been busy job hunting and in the lab. I just noticed this post.

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