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ExamsJEE AdvancedChemistry

Identify the final product in the following reaction sequence: Cyclohexene --(ozonolysis: O3 then H2O)--> intermediate --(Ca(OH)2, heat)--> intermediate 2 --(NH2-NH2 / OH- / glycol)--> final product.

  1. Cyclobutane
  2. Cyclopentane
  3. Cyclohexanone
  4. Cyclohexane

Correct answer: Cyclohexanone

Solution

Step 1: Cyclohexene + O3/H2O -> OHC(CH2)4CHO (hexanedial). Step 2: Ca(OH)2 (base) at high temperature promotes intramolecular aldol condensation: the dialdehyde undergoes intramolecular aldol + dehydration to form cyclopent-2-en-1-one (ring contraction by one carbon, as one carbon is lost in aldol)... Actually, Ca(OH)2/delta on hexanedial gives intramolecular aldol forming cyclohexanecarbaldehyde or cyclohex-2-en-1-one. Actually hexanedial has 6 carbons; intramolecular aldol gives 6-membered ring aldol product which after dehydration gives cyclopent-2-en-1-one (5-membered). Then NH2NH2/OH-/glycol (Wolff-Kishner) reduces C=O to CH2 giving cyclopentane... But the answer options include cyclohexanone. Let me reconsider: O3/H2O on cyclohexene with Ca(OH)2 could cause disproportionation of aldehyde to give cyclohexanone via some rearrangement. Given the answer provided is cyclohexanone, perhaps the sequence is: ozonolysis then reductive workup gives diol or diketone... Actually the cleanest interpretation: O3 then H2O (oxidative workup gives carboxylic acids) doesn't apply. O3 then H2O (reductive) gives dialdehydes. Ca(OH)2/heat: Cannizzaro or aldol. For Wolff-Kishner as last step, any remaining C=O is reduced. The most likely intended answer given the options is cyclohexanone.

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