Question

The reaction, [R]c1ccc(C(Br)Nc2ccccc2)cc1 is influenced by the hyperconjugative effect of group R. Now if R sequentially is I. \(\mathrm{CH}_{3}\) II. \(\mathrm{C}_{2} \mathrm{H}_{5}\) III. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CH}\) IV. \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{C}\) The increasing order of speed of the above reaction shall be in the sequence (a) I, IV, II, III (b) I, II, III, IV (c) I, III, II, IV (d) IV, I, II, III

Short answer

The correct sequence is (a) I, IV, II, III.

Step-by-step solution

Understand the role of hyperconjugation

Hyperconjugation is an effect where electron-donating groups stabilize a reaction intermediate like a carbocation through delocalization. In this context, the alkyl groups can donate electron density to stabilize a transition state or intermediate, enhancing the reaction speed.

Evaluate the hyperconjugative potential of each R group

Compare each R group based on the number of hyperconjugative hydrogen atoms (hydrogens on adjacent carbon atoms) they provide. Larger groups provide more hyperconjugative interactions: - I: \({\rm CH}_3\) has 3 hyperconjugative hydrogens.- II: \({\rm C}_2{\rm H}_5\) has 6 hyperconjugative hydrogens.- III: \((\rm {CH}_3)_2{\rm CH}\) has 9 hyperconjugative hydrogens.- IV: \(\left({\rm CH}_3\right)_3{\rm C}\) has 9 hyperconjugative hydrogens and steric hindrance that slightly reduces its overall effectiveness.

Determine the sequence based on stabilization ability

The group with the highest hyperconjugative interaction generally increases reaction speed the most. Accounting for \({\rm CH}_3\), \({\rm C}_2{\rm H}_5\), \(\left({\rm CH}_3\right)_2{\rm CH}\), the methyl group has the least interactions, while the tertiary butyl group offers the most but is slightly hindered by sterics.

Rank the groups based on reaction speed enhancement

Given the number of hyperconjugative hydrogen interactions and the slight steric effects, the order of increasing reaction speed is: \(\left({\rm CH}_3\right)_3{\rm C} < {\rm CH}_3 < {\rm C}_2{\rm H}_5 < (\rm {CH}_3)_2{\rm CH}\), which corresponds to option (a) I, IV, II, III.

Key concepts

Carbocation Stability

Understanding carbocation stability is crucial in organic chemistry, as it influences the reaction rate and mechanism. A carbocation is a positively charged carbon atom that is often an intermediate in organic reactions. It is highly unstable due to its deficiency of electrons, making it eager to find ways to stabilize itself. One major way it achieves stability is through hyperconjugation.

In hyperconjugation, adjacent alkyl groups help stabilize the carbocation by delocalizing their electron clouds toward the empty p-orbital of the carbocation. This delocalization of electrons reduces the positive charge on the carbocation, making the entire molecule more stable.

When we consider different alkyl groups, the number of these electron-donating hydrogen atoms in each group can significantly alter how stable the carbocation becomes.

• More attached hydrogens can increase the hyperconjugative effect, leading to a stronger stabilization of the carbocation.
• The result of increased stability is an enhancement in reaction speed, as the transition state becomes less energetically demanding.

Thus, the concept of carbocation stability is intertwined with reaction mechanisms, directly affecting the potential pathways and speed of chemical reactions.

Reaction Mechanism

The reaction mechanism in organic chemistry describes the step-by-step process by which reactants are transformed into products. Understanding this mechanism is key to predicting how changes in molecular structure can impact reaction speed, as showcased when evaluating the hyperconjugative effect.

When dealing with carbocations, the reaction mechanism can heavily rely on stabilizing interactions. As a carbocation is highly unstable, the molecule's flexibility to undergo further reactions is often dictated by how it can stabilize itself.

Through hyperconjugation, electron-rich regions of the molecule act as a cushion for the electron-deficient carbocation, anchoring it enough to proceed further in the reaction pathway. If we take our specific example of varying alkyl groups attached, each variation can trigger different stabilization routes:

• The methyl \( ext{CH}_3\) group offers the least hyperconjugative stabilization, meaning less effective in speeding up the reaction.
• Ethyl \( ext{C}_2 ext{H}_5\) and isopropyl \(( ext{CH}_3)_2 ext{CH}\) groups provide more hyperconjugative interactions, allowing smoother reaction progression.

The ability to predict the speed and pathway of the reaction based on the presence of hyperconjugative groups emphasizes the importance of understanding these fundamental mechanisms.

Organic Chemistry Concepts

Organic chemistry features many pivotal concepts that help in understanding how complex molecules interact, transform, and stabilize. Some of these concepts are key when contemplating the effects of hyperconjugation. Hyperconjugation is one such phenomenon where the dynamics of electron distribution and molecular stability are highlighted.

When discussing hyperconjugation, it is part of the larger topic of electronic effects within molecules. These effects are crucial as they help chemists predict physical characteristics, chemical behavior, and reactivity patterns of organic molecules.

For instance, hyperconjugation is closely related to:

• Resonance, where electron clouds delocalize across different parts of a molecule for extra stability.
• Inductive effects, where a permanent charge or dipole is created due to differences in electronegativity between atoms in a molecule, affecting reactivity.

Understanding these foundational concepts allows chemists to forecast reaction outcomes accurately and design experiments that align with desired results, making the overarching study of organic chemistry not only complex but also highly logical and predictable.