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Topic: {Acetolysis} of Bridgehead Sulfonates  (Read 2748 times)

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Offline suhoca

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{Acetolysis} of Bridgehead Sulfonates
« on: May 06, 2018, 06:17:28 PM »
I'm trying to explain the relative rates of these different bridgehead sulfonates.
I would have thought that the norbene derivatives would have had a faster rate because they can form a norbenyl cation - but apparently not.
Any tips very much appreciated.

{Mod Edit: typo}
« Last Edit: May 07, 2018, 02:57:56 PM by Arkcon »

Offline pgk

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Re: Acetonlysis of Bridgehead Sulfonates
« Reply #1 on: May 07, 2018, 02:20:14 PM »
Think about steric hindrance.
PS: “Acetolysis” and not “Acetonlysis”, neither “Acetonolysis”.
« Last Edit: May 07, 2018, 03:02:24 PM by pgk »

Offline pgk

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Re: {Acetolysis} of Bridgehead Sulfonates
« Reply #2 on: May 08, 2018, 01:09:57 PM »
Thinking twice and given that students ought to answer questions and not to criticize or to revise the said questions, I think it is more correct to accept that acetonolysis (solvolysis) of the bicyclo-norbonyl/norbornenyl alkylosulfonate esters occurs hereby and not their acetolysis.
Besides, the formation of a norbornane/norbornene cation is possible because it is favored on the bridgehead carbon atoms of bridged rings, regardless if being secondary ones:
Bridgehead solvolytic reactivity. A unified data set to test molecular mechanics, J. Org. Chem., (1985), 50(26), 5852-5855
https://pubs.acs.org/doi/abs/10.1021/jo00350a080
« Last Edit: May 08, 2018, 03:01:38 PM by pgk »

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