Question

Aryl halides are less reactive towards nucleophilic substitution reactions as compared to alkyl halides due to 1\. the formation of less stable carbonium ion 2\. resonance stabilization 3\. longer carbon-halogen bond 4\. the inductive effect 5\. sp \(^{2}\) hybridized carbon attached to halogen (a) \(1,2,3\) (b) \(2,4,5\) (c) 2,5 (d) 4,5

Short answer

(c) 2,5

Step-by-step solution

Understanding Aryl Halides Reactivity

Aryl halides are compounds where a halogen atom is bonded to an aromatic ring. They are known to be less reactive towards nucleophilic substitution reactions than alkyl halides. This is mainly due to the structural and electronic properties of the aromatic system that hinder such reactions.

Evaluate Resonance Stabilization (Option 2)

In aryl halides, the lone pair of electrons on the halogen atom is delocalized into the aromatic ring through resonance. This stabilization through resonance makes it difficult for the halide to leave the aromatic ring, thereby reducing reactivity towards nucleophilic substitution.

Evaluate the Role of sp² Hybridization (Option 5)

The carbon atom in the C-X bond in aryl halides is sp² hybridized. This makes the bond stronger and shorter compared to the sp³ hybridized carbon in alkyl halides, making it more difficult for the bond to break and for nucleophilic substitution to occur.

Cross Out Incorrect Options

1. Formation of less stable carbonium ion is irrelevant here since aryl halides don’t typically form such ions. 3. Longer carbon-halogen bond is incorrect since aryl carbon-halogen bonds are shorter. 4. While inductive effects exist, they are less influential in this context. Thus, options 1, 3, and 4 do not contribute to reduced reactivity in the significant way that resonance stabilization and sp² hybridization do.

Selecting the Correct Answer

After evaluating each provided reason and considering the significant influence of resonance stabilization and the sp² hybridization of the carbon, options dealing with these (2 and 5) are correct. Therefore, choice (c) 2, 5 is the best fit.

Key concepts

Resonance Stabilization

In aryl halides, the presence of a halogen atom attached to an aromatic ring plays a significant role in its chemical behavior. One of the crucial aspects of this is resonance stabilization. The halogen atom in an aryl halide possesses a lone pair of electrons. These electrons can participate in resonance with the aromatic ring, delocalizing across the entire system. This delocalization provides a stabilizing effect, which effectively holds the halide in place, making it less feasible for any substitution to occur.

Resonance stabilization in aryl halides can be visualized in terms of resonance structures, where the lone pair on the halogen atom can be delocalized across the pi system of the benzene ring. This creates partial double-bond character to the carbon-halogen bond, thereby strengthening the bond and reducing the possibility of the halogen atom leaving.

• This added stability through electron delocalization means that the carbon-halogen bond is tougher to break.
• Resonance not only stabilizes an aryl halide but also poses a challenge for a nucleophile to effectively kick out the halogen atom.

Ultimately, this resonance stabilization is a key contributor to the reduced reactivity of aryl halides in nucleophilic substitution reactions.

sp² Hybridization

The hybridization of the carbon atom bonded to the halogen in aryl halides is another important factor that affects reactivity. In aryl halides, the carbon atom bonded to the halogen is \ \( sp^{2} \ \) hybridized. This type of hybridization results in a stronger and shorter bond compared to an \ \( sp^{3} \ \)-hybridized carbon, which is typically found in alkyl halides.

The \ \( sp^{2} \ \) hybridization leads to a bond with more s-character, which results in not only a more robust bond but also enhances overlap between the carbon and halogen atoms. This tight bonding means greater energy is required to break such a bond, significantly reducing the chance of a nucleophilic substitution.

• The shorter and stronger C-X bond due to \ \( sp^{2} \ \) hybridization makes bond cleavage more challenging during reactions.
• Consequently, this structural feature contributes to the lower reactivity of aryl halides toward nucleophilic attacks.

Thus, \ \( sp^{2} \ \) hybridization is a fundamental aspect in understanding why aryl halides display decreased reactivity in nucleophilic substitution reactions.

Aryl Halides Reactivity

The reactivity of aryl halides in nucleophilic substitutions is notoriously lower compared to their alkyl counterparts. Understanding the reasons tied to resonance stabilization and \ \( sp^{2} \ \) hybridization provides insights into this phenomenon.

Aryl halides, due to their structural configuration, resist typical nucleophilic substitution. The aromatic ring provides resistance, stabilizing the compound and reducing the likelihood of substitution.

• The aromatic core resists disruption because it features a highly delocalized \ \( \pi \)-electron system.
• The combination of resonance stabilization and \ \( sp^{2} \ \)-hybridized carbons enhances bond strength and durability.

With these factors at play, aryl halides not only resist the typical nucleophilic substitution pathway but often require harsher conditions or alternative methods for modification. Understanding these intrinsic properties is essential for utilizing aryl halides effectively in chemical synthesis and reactivity.