Question

Which of the following undergoes nucleophillic substitution exclusively by \(\mathrm{SN}^{1}\) mechanism? (a) ethyl chloride (b) isopropyl chloride (c) chlorobenzene (d) benzyl chloride

Short answer

Benzyl chloride undergoes SN1 exclusively due to resonance stabilization.

Step-by-step solution

Understand the SN1 Mechanism

The SN1 mechanism involves a two-step process where the leaving group departs before the nucleophile attacks. This mechanism is favored in substrates that form stable carbocations after the leaving group departs. Typically, tertiary carbons or benzylic carbons stabilize the carbocation well due to resonance or hyperconjugation effects.

Analyze Ethyl Chloride

Ethyl chloride (th_3CH_2Cl) is a primary alkyl halide. Primary carbocations are not stable because there are no adjacent carbon atoms to stabilize the positive charge through hyperconjugation or resonance. Therefore, it does not favor the SN1 mechanism.

Examine Isopropyl Chloride

Isopropyl chloride ((CH_3)_2CHCl) is a secondary alkyl halide. Secondary carbocations are more stable than primary ones, but they are less stable compared to tertiary or benzylic carbocations. Therefore, isopropyl chloride may undergo SN1 but not exclusively.

Evaluate Chlorobenzene

Chlorobenzene (C_6H_5Cl) contains a chlorine atom bound to a benzene ring. The aromatic ring stabilizes the structure, and the carbon-chlorine bond is part of the pi system. Hence, chlorobenzene does not form a carbocation easily and does not undergo nucleophilic substitution by SN1 mechanism.

Consider Benzyl Chloride

Benzyl chloride (C_6H_5CH_2Cl) is a primary alkyl halide, but it forms a particularly stable carbocation due to resonance stabilization by the aromatic ring. This makes benzyl chloride favorable for SN1 reactions, as the intermediate carbocation is stabilized.

Conclusion

Based on the stability of the carbocation intermediates, benzyl chloride undergoes nucleophilic substitution exclusively by the SN1 mechanism. It forms the most stable carbocation due to resonance, unlike the other options.

Key concepts

Carbocation Stability

The structure and stability of carbocations play a crucial role in determining the pathway of certain chemical reactions, particularly the SN1 mechanism. In these reactions, the substrate forms a carbocation, a positively charged carbon atom, when the leaving group departs from the molecule. The formation of a stable carbocation ensures that the reaction is more likely to proceed.

The stability of carbocations is affected by several factors, including:

• Degree of Carbon Substitution: Tertiary carbocations, involving three alkyl groups attached to the carbon, are more stable than secondary or primary ones due to greater hyperconjugation.
• Resonance: Carbocations that can be stabilized by resonance, where delocalization of electrons occurs, tend to be more stable. This is particularly true in benzylic carbocations.
• Hyperconjugation: The overlap of adjacent Sigma-bonding electrons can delocalize the positive charge over the atomic structure, adding to the stability.

Understanding the nuances of carbocation stability helps in predicting the feasibility of SN1 reactions among different substrates.

Resonance Stabilization

In organic chemistry, resonance stabilization is a key concept that explains the distribution of electrons across a molecule, contributing to its overall stability. Resonance occurs when there is a possibility to draw two or more valid Lewis structures (resonance structures) for a molecule, which differ only in electron arrangements, not the atom positions.

This phenomenon is particularly important in the context of the SN1 mechanism. Some carbocations, like benzylic carbocations, achieve additional stability through resonance:

• In benzylic carbocations, the positive charge is delocalized over the aromatic ring. As a result, the molecule is more stable compared to carbocations lacking this feature.
• The resonance structures depict the positive charge being distributed across multiple atoms, leading to a lowering of energy and increased stability.

Resonance stabilization is hence an impactful factor that lowers the energy barrier for the formation and persistence of an intermediate carbocation in SN1 reactions.

Nucleophilic Substitution

Nucleophilic substitution is a broad class of reactions in organic chemistry where a nucleophile, an electron-rich species, replaces a leaving group, typically a halogen, in a molecule. The SN1 and SN2 mechanisms dictate how this substitution occurs, with differing pathways and kinetics.

• SN1 (Unimolecular Nucleophilic Substitution): This occurs in two distinct steps - formation of a carbocation intermediate and subsequent attack by the nucleophile. The first step is rate-determining, and the reaction rate depends only on the substrate concentration.
• SN2 (Bimolecular Nucleophilic Substitution): Occurs in a single step with simultaneous attack by the nucleophile and departure of the leaving group. Reaction rate is influenced by both substrate and nucleophile concentrations.

Understanding the nature of the substrate and the environment gives crucial insights into which mechanism will predominate in a given reaction - SN1 or SN2. Particularly, substrates that form stable carbocations often tend towards SN1 pathways, where the stability of the intermediate is vital.

Alkyl Halides

Alkyl halides, also known as haloalkanes, are a group of compounds derived from alkanes with one or more halogen atoms substituted for hydrogen atoms. These molecules are particularly interesting in organic chemistry for their roles in nucleophilic substitution reactions.

• Classification: Alkyl halides can be primary, secondary, or tertiary, depending on the number of carbon atoms attached to the carbon currently bonded to the halogen. This classification impacts their reactivity.
• Reactivity in SN1 and SN2: Primary alkyl halides are generally less reactive in SN1 mechanisms due to their inability to form stable carbocations, while secondary and tertiary are more favorable. But, benzylic halides, though primary, are an exception due to resonance stabilization.
• Solvent Effects: The choice of solvent also affects reactions of alkyl halides. Polar protic solvents are preferred for SN1 as they stabilize the charged intermediates and accelerate the reaction process.

In summary, understanding the nature of alkyl halides is essential in predicting and explaining their behavior in nucleophilic substitution reactions like SN1.