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Question #44942

Difficulty: 8/10 | 🟢 Free

The Question

Consider the following statements regarding the structural, thermodynamic, and acid-base properties of nitrogenous compounds at 298 K298\text{ K}:

\begin{enumerate} \item[(I)] 2,62,6-Dimethyl-N,NN,N-dimethylaniline is a stronger base than 3,53,5-dimethyl-N,NN,N-dimethylaniline because the bulky \textit{ortho}-methyl groups force the −NMe2-\text{NMe}_2 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 pKbpK_b of 22-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 260 nm260\text{ nm} 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

SubjectChemistry
ChapterAmines - Class 12
ConceptOrtho-Effect in Anilines
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree