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Question #44942
The Question
Consider the following statements regarding the structural, thermodynamic, and acid-base properties of nitrogenous compounds at :
\begin{enumerate} \item[(I)] -Dimethyl--dimethylaniline is a stronger base than -dimethyl--dimethylaniline because the bulky \textit{ortho}-methyl groups force the group out of the ring plane, preventing the delocalization of the nitrogen lone pair. \item[(II)] In aqueous solution, the lactim (enol) tautomer of Uracil is thermodynamically favored over the lactam (keto) tautomer due to the attainment of complete Hückel aromaticity in the pyrimidine ring. \item[(III)] The of -methylaniline is higher than that of aniline due to the 'ortho-effect', which arises primarily from the steric hindrance to the hydration of the resulting anilinium cation. \item[(IV)] The thermal denaturation of DNA results in a hyperchromic shift at due to the disruption of hydrogen bonds and base stacking, while the covalent phosphodiester backbone remains intact. \end{enumerate}
Which of the following combinations of statements is CORRECT?
Options
- A.
I, III, and IV
- B.
I, II, and III
- C.
II, III, and IV
- D.
I, II, and IV
Check Your Answer
Correct Answer
Step-by-Step Solution
Explanation
How the Examiner Thinks
Exception_Exposure
Learn to identify edge cases and boundary exceptions that JEE examiners hide in math problems.
Concepts Behind This Question
Ortho-Effect in Anilines|Nitrogenous Base Keto-Enol Tautomerism|Protein Denaturation Specificity
Why This Question Is Tricky
Common Mistakes
This question tests the student's ability to distinguish between kinetic/structural hindrance and thermodynamic tautomeric preference.
A common trap is assuming that aromaticity is the ultimate driving force for stability, leading students to incorrectly predict that nucleobases like Uracil exist in their enol (lactim) forms to maximize aromaticity.
However, the thermodynamic stability of the keto (lactam) form, driven by strong C=O bond energy and favorable solvent hydrogen bonding, outweighs the aromatic stabilization.
Furthermore, it tests the nuanced difference between the 'ortho-effect' in primary anilines (which decreases basicity due to steric hindrance to solvation) and 'Steric Inhibition of Resonance' (SIR) in N,N-dialkylanilines (which increases basicity by localizing the lone pair).
Quick Facts About This Question
Question Information
| Subject | Chemistry |
| Chapter | Amines - Class 12 |
| Concept | Ortho-Effect in Anilines |
| Difficulty | 8 |
| Cognitive Load | 7 |
| Target Solve Time | 160 sec |
| Access | Free |