4
$\begingroup$

Why is cyclopentadiene more reactive than 9-anthracenemethanol when acting as a diene?

Both molecules are locked in an s-cis conformation, which is favourable. I'm thinking that it's due to the extensive conjugation in 9-anthracenemethanol?

$\endgroup$
4
$\begingroup$

Yes, you are exactly right. Anthracene is better described by this structure (where there are no fixed single and double bonds, but rather a delocalized aromatic structure)

enter image description here

than a structure like this (where the single and double bonds are fixed and distinct from one another).

enter image description here

So in anthracene, the aromatic character must be disrupted to some degree in order to undergo the Diels-Alder reaction. In cyclopentadiene, there is no aromaticity to disrupt, the double bonds are basically fixed like in buta-1,3-diene (and, as you point out, locked in the required s-cis conformation).

A final note, benzene won't undergo a Diels-Alder under normal conditions because its aromaticity is completely disrupted and lost during the process. In anthracene the aromaticity remains in two of the rings, a much smaller price to pay.

$\endgroup$
  • $\begingroup$ Thank you ron. I'm still co fused about the need for 3 molar equivalents of n-methylmaleimide versus 1 molar equivalent of 9-anthracenemethanol? $\endgroup$ – Edward Feb 22 '15 at 13:28
  • $\begingroup$ In organic solvents a 1:1 ratio of diene to dienophile is typically used. Are you running your reaction in water? The reactants are less soluble in water and therefore tend to cluster around themselves, effectively increasing their concentration and accelerating the reaction. Because the maleimide does have some solubility in water an excess is used so that there is 1 equivalent of maleimide that is not dissolved in the water and available to react with the 9-anthracenemethanol outside of the water. $\endgroup$ – ron Feb 22 '15 at 15:17

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.