Q30.

Question



Question: The cis ketone A is isomerized to a trans ketone B with aqueous NaOH. A similar isomerization does not occur with ketone C. (a) Draw the structure of B using a chair cyclohexane. (b) Label the substituents in C as cis or trans, and explain the difference in reactivity.

Step-by-Step Solution

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Answer

 

(a) The structure of B using chair cyclohexane is shown below:


              Trans isomer


(b) The substituents in C is labeled below:

The reactivity of the cis form is more than its trans counterpart.


1Step 1: Isomerization in the presence of NaOH



In the presence of a base (NaOH), the cis isomer converts to a trans isomer because the acetyl group is present in the axial position; hence, it suffers from the syn-diaxial interaction.  This is not the case in the trans isomer where it occupies the equatorial position and hence does not suffer from syn-diaxial interaction.



Representation of the interconversion from cis to trans in the presence of a base


2Step 2: Rate of reactivity


The cis form is more reactive than the trans form because when the sp2  carbon of the acetyl group converts to sp3 carbon in the presence of a nucleophile, it does not suffer from syn-diaxial interaction as compared to its trans counterpart.


Representation of the nucleophilic attack on the cis and trans form

3Step 3: The answer for the given solution



(a) The structure of B using chair cyclohexane is shown below:


                Trans isomer

        Representation of the trans isomer

(b) The substituents in C are labeled below:


      Representation of the cis isomer

The reactivity of the cis form is more than its trans counterpart.