Question 1
Epoxides are classified as ethers, but their reactivity is dramatically different from that of acyclic ethers like diethyl ether. What structural feature of an epoxide is primarily responsible for this enhanced reactivity?
- The sp² hybridization of the oxygen atom, which weakens the C-O bonds.
- The presence of two lone pairs on the oxygen, which increases its nucleophilicity.
- The significant angle strain in the three-membered ring, which is relieved upon ring-opening. (correct answer)
- The inductive effect of the carbon atoms, which makes the oxygen a better leaving group.
Explanation: Epoxides are three-membered rings containing an oxygen atom. The ideal bond angle for an sp³ hybridized atom is 109.5°. In an epoxide, the internal bond angles are forced to be approximately 60°, creating substantial angle strain. Nucleophilic attack on one of the carbons of the epoxide leads to ring-opening, which relieves this strain. This relief of strain is a powerful thermodynamic driving force for the reaction, making epoxides much more reactive than their acyclic, strain-free ether counterparts. The oxygen is sp³ hybridized (A). While it has lone pairs (B), so do other ethers. The inductive effect (D) is not the primary reason for the unique reactivity.
Question 2
A student encounters two constitutional isomers with formula C₄H₈O₂: ethyl acetate and butyric acid. When planning to separate these compounds, which difference in their functional group properties would be most practically useful for achieving clean separation?
- The difference in boiling points due to hydrogen bonding capabilities
- The difference in acid-base behavior allowing aqueous extraction (correct answer)
- The difference in nucleophilic substitution reactivity patterns
- The difference in polarity affecting chromatographic separation
Explanation: Ethyl acetate (ester) and butyric acid (carboxylic acid) differ dramatically in acid-base behavior. Butyric acid is acidic and will dissolve in aqueous NaOH to form the water-soluble sodium salt, while ethyl acetate remains neutral and stays in the organic layer. This allows easy separation by acid-base extraction. Choice A is less practical because both compounds have similar boiling points. Choice C describes chemical reactions rather than separation methods. Choice D is less practical than simple acid-base extraction for preparative separation.
Question 3
Which of the following functional groups, when present in a molecule, constrains at least four contiguous non-hydrogen atoms to lie in the same plane?
- A secondary alcohol
- A terminal alkyne
- A simple thioether (sulfide)
- A secondary amide (correct answer)
Explanation: Due to resonance between the nitrogen lone pair and the carbonyl pi bond, the C-N bond of an amide has significant double-bond character. This restricts rotation and forces the carbonyl carbon, the oxygen, the nitrogen, and the atoms directly attached to them to be coplanar. In a secondary amide (R-C(=O)NH-R'), the oxygen, carbonyl carbon, nitrogen, and the first carbon of each R group (assuming they are not H) are all held in a plane. A terminal alkyne (B) forces four atoms (R-C≡C-H) into a linear arrangement, which is a plane, but this includes a hydrogen atom. A secondary alcohol (A) and a thioether (C) have sp³ hybridized central atoms, leading to tetrahedral (non-planar) geometries.