Question

Arrange in order of decreasing trend towards \(\mathrm{S}_{\mathrm{E}}\) reactions: (I) chlorobenzene (II) benzene (III) anilinium chloride (IV) toluene (a) IV \(>\mathrm{II}>\mathrm{I}>\mathrm{III}\) (b) \(\mathrm{I}>\mathrm{II}>\mathrm{III}>\mathrm{IV}\) (c) \(\mathrm{II}>\mathrm{I}>\mathrm{III}>\mathrm{IV}\) (d) III \(>\mathrm{I}>\mathrm{II}>\mathrm{IV}\)

Short answer

The answer is (a) IV > II > I > III, as the ranking is based on the activating or deactivating nature of the substituents.

Step-by-step solution

Understand the Concept of SE Reactions

SE reactions, or electrophilic aromatic substitution reactions, occur when an electrophile replaces a hydrogen atom on an aromatic ring. The rate of SE reactions is influenced by the nature of substituents on the aromatic ring that can either activate or deactivate the ring towards electrophilic attack. Activating substituents increase the rate, while deactivating ones decrease it.

Analyze Each Compound's Structure and Groups

- **Chlorobenzene (I):** Contains a chlorine atom, which is a deactivating group due to its electron-withdrawing inductive effect, though slightly activating through resonance. - **Benzene (II):** Has no substituents, offering a baseline reactivity. - **Anilinium chloride (III):** Contains an ammonium ion, a highly deactivating group because it strongly withdraws electrons. - **Toluene (IV):** Contains a methyl group, which is activating due to its electron-donating nature through hyperconjugation.

Rank Based on Activating and Deactivating Effects

Consider the activating and deactivating effects of the groups attached to the benzene ring: - **Toluene (IV):** The methyl group strongly activates the benzene ring. - **Benzene (II):** With no substituents, it is neutral. - **Chlorobenzene (I):** Deactivated by chlorine, but less so than anilinium chloride. - **Anilinium chloride (III):** Strongly deactivated by the ammonium ion.

Establish Order of Reactivity

The order of reactivity reflects the degree to which the substituents activate or deactivate the benzene ring: - Toluene has the most activating effect. - Chlorobenzene is less reactive than benzene due to the weak deactivating effect of chlorine. - Anilinium chloride is the least reactive. Thus, the order is increasingly deactivating: **IV > II > I > III**.

Key concepts

Activating and Deactivating Groups

Activating and deactivating groups play a crucial role in the reactivity of aromatic compounds during electrophilic aromatic substitution (SE) reactions. These groups can either enhance or reduce the reaction rate by influencing the electron density of the benzene ring.
Understanding the behavior and effects of these groups can reveal why certain aromatic compounds react faster or slower in SE reactions.
**Activating Groups**

• Increase the electron density of the aromatic ring, making it more prone to electrophilic attack.
• Generally possess electron-donating properties, such as those seen with alkyl groups (e.g., methyl group in toluene).
• Can stabilize the intermediate cation formed during the reaction, increasing reaction speed.

**Deactivating Groups**

• Decrease the electron density of the ring, thereby reducing the susceptibility to electrophiles.
• Often have electron-withdrawing features, such as the ammonium ion in anilinium chloride or the chlorine atom in chlorobenzene.
• Make the aromatic ring less stable during the reaction, thus slowing down the reaction rate.

By recognizing these effects, we can predict the relative reactivities of different substituted benzene compounds.

Aromatic Compounds

Aromatic compounds are a fascinating class of molecules characterized by a unique arrangement of atoms and electrons. At their core is the benzene ring, a hexagonal ring of six carbon atoms held together by alternating single and double bonds, often represented by a circle in its chemical structure.
These compounds exhibit remarkable stability due to **aromaticity**, a concept rooted in resonance.
**Key Characteristics**

• The electrons in the double bonds are delocalized over the ring, creating a stable orbital structure known as a pi system.
• This delocalization leads to lowered energy and a characteristic resilience to reactions that would typically alter unsaturated compounds.
• Aromatic compounds are prevalent in both natural and synthetic chemistry, forming the backbone of many drugs, dyes, and polymers.
• Their stability makes them foundational in organic chemistry, where they undergo specific reactions like electrophilic aromatic substitution.

Understanding aromatic compounds helps in predicting how they might react in various chemical processes, such as the addition of electrophiles in SE reactions.

Chemical Reactivity

Chemical reactivity in aromatic compounds, especially in terms of electrophilic aromatic substitution (SE) reactions, is determined by how substituents on the ring influence its electronic environment. This interaction dictates whether a compound will react quickly or slowly with electrophiles.
**Influences on Reactivity**

• Activating groups boost the ring's electron density, making it more attractive to electrophiles, hence increasing reactivity.
• Deactivating groups, conversely, draw electrons away, making the compound less reactive.
• Neutral aromatic compounds like benzene provide a baseline to measure reactivity against, as seen in the comparison of chlorobenzene, toluene, and anilinium chloride.

**Practical Implications**

• In industrial applications, controlling the rates of SE reactions is crucial for optimizing production processes involving aromatic compounds.
• Synthetic chemists often exploit these reactivity trends to design and execute complex organic syntheses effectively.
• Understanding these reactivity principles aids in predicting outcomes and designing experiments that control or exploit electrophilic reactions on aromatic rings.

A mastery of chemical reactivity concepts allows chemists to anticipate and manipulate the behavior of aromatic compounds in various chemical settings.