Reaction of perchloric acid with cyclopropenol

Question

Question:

Identify A and B.

My attempt

The first step will be the attack of $\ce{PhMgX}$ on carbonyl carbon, that is, 1,2 position followed by hydrolysis, yielding an alcohol.

But how does the reaction proceed with $\ce{HClO4}$?

you should read about cyclopropenyl cation in aromaticity section of advanced organic books. HClO4 is a strong protonating agent and should protonate OH-group, that will leave. The remaining cation is known to be remarkably stable in organic chemistry and have stable salts. — permeakra, May 19 '15 at 00:05
@permeakra it is remarkably stable yes, but getting rid of the strained ring by oxidative cleavage (similar to hot $\ce{KMnO4}$) seems way more plausible. We shouldn't ignore the oxidative capabilities of $\ce{HClO4}$ — napstablook, Jul 25 '21 at 04:31
The answer provided is wrong . Whenever cyclic conjugated ketones comes in question then the conjugation is the unsaturated part is the point of action. Which means double bond will be attacked. — rajendra dubey, Aug 24 '21 at 04:46

score 7 · Answer 1 · edited Mar 02 '18 at 10:33

7

The first step is indeed 1,2-addition of the Grignard reagent to the keto group, and product A is the alcohol:

Treatment of the alcohol with the strong acid $\ce{HClO4}$ cannot yield the usual dehydration product (alkene) in this case, as the corresponding alkene would have two double bonds in an already highly strained three-membered ring, which is highly unfavorable. Instead, after protonation of the $\ce{OH}$ group and subsequent loss of $\ce{H2O}$, the carbocation:

is obtained as the final product B (with $\ce{ClO4-}$ being the counteranion). The planar cyclopropenyl cation is a Hückel aromatic compound with $(4 \cdot 0+2) = 2$ $\pi$ electrons, and delocalization of the positive charge over the two phenyl substituents can provide further stabilization.

edited Mar 02 '18 at 10:33

Gaurang Tandon

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answered Nov 10 '15 at 14:15

Jannis Andreska

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Carbocation as the final product, really interesting! – Archer Jul 11 '18 at 20:21
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Yes this happens when the intermediate is highly stable with a stable ion like flouro borate, perchlorate etc. (Note that stable counter ion makes the ionic compound to be formed easily according to fajan's rules – An enthusiast Apr 23 '20 at 16:16
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@Archer I think this answer disregards $\ce{HClO4}$'s oxidative abilities. I think the stability gained by cleaving the alkene is far more than the resonance of the carbocation. – napstablook Jul 07 '21 at 16:08
@napstablook $\ce{HClO4}$ is often used in dilute solution where it dissociates, and then the oxidation power of the perchlorate ion is kinetically squashed. Perchloric acid here is acting only as an acid. – Oscar Lanzi Aug 24 '21 at 15:59

Reaction of perchloric acid with cyclopropenol

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