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CIE A-Level Chemistry Study Notes

34.2.2 Reactions of Phenylamine

Phenylamine, also known as aniline, is a pivotal organic compound in the field of chemistry, primarily in dye and pharmaceutical production. This comprehensive guide delves into its key reactions: bromination, diazonium salt formation, and azo compound synthesis.

Introduction to Phenylamine

Phenylamine, with its benzene ring attached to an amino group, stands as a cornerstone in organic chemistry. Its unique structure makes it particularly interesting for various chemical reactions.

  • Structure and Properties: Phenylamine's structure comprises a benzene ring bonded to an NH2 group. This structure imparts distinctive chemical properties, making it more reactive than benzene in certain reactions.
  • Significance in Chemistry: Its role in the manufacture of dyes, drugs, and polymers underscores its importance in industrial and academic chemistry.
Structure of aniline or Phenylamine

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Bromination of Phenylamine

Bromination is a reaction where bromine atoms are introduced into a compound. Phenylamine undergoes bromination more readily than benzene due to the activating effect of the amino group.

Mechanism

  • Electrophilic Aromatic Substitution: The amino group makes the benzene ring more susceptible to electrophilic attack. The reaction does not require a catalyst, unlike bromination of benzene.
  • Regioselectivity: Bromination primarily occurs at the ortho and para positions relative to the NH2 group.

Products

  • 2,4,6-Tribromophenylamine: This is the predominant product, with bromine atoms at the ortho and para positions.
Structure of 2,4,6-Tribromophenylamine

Structure of 2,4,6-Tribromophenylamine

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Formation of Diazonium Salts

The formation of diazonium salts from phenylamine is a pivotal reaction, particularly in the synthesis of aromatic compounds.

Reaction Conditions

  • Temperature Sensitivity: The reaction is carried out at temperatures below 5°C to stabilize the diazonium salt.
  • Acid Choice: Typically, nitrous acid is used, generated from sodium nitrite and a strong acid like hydrochloric acid.

Mechanism

  • Nitrosation Reaction: Phenylamine reacts with nitrous acid to form a diazonium salt, releasing water as a byproduct.

Products

  • Benzene Diazonium Chloride: This compound serves as an intermediate for further reactions, including azo coupling.
The formation of diazonium salts from phenylamine

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Synthesis of Azo Compounds

Azo compounds, characterized by their vivid colours, are synthesized through a series of reactions starting from phenylamine.

Step 1: Formation of Diazonium Salt

  • This step is identical to the formation of diazonium salts as previously described.

Step 2: Coupling Reaction

  • Alkaline Conditions: The reaction is conducted in an alkaline environment to facilitate coupling.
  • Reactants: Typically, phenol or another aromatic compound reacts with the diazonium salt.
  • Mechanism: The diazonium salt undergoes a nucleophilic aromatic substitution with the phenol, forming the azo bond.

Products

  • Azo Dyes: These compounds are noted for their stability and vibrant colours, making them ideal for textile dyes.
Aniline reaction with diazonium salts to form 4-(phenyldiazenyl)aniline (azo dyes)

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Basicity of Phenylamine

Phenylamine's basicity significantly affects its reactivity in the aforementioned reactions.

Comparison with Other Amines

  • Less Basic than Aliphatic Amines: Due to the resonance stabilization of the lone pair on the nitrogen with the aromatic ring, phenylamine is less basic than simple aliphatic amines like ethylamine.

Effect on Reactions

  • Electrophilic Substitution Reactions: Its reduced basicity compared to aliphatic amines affects its susceptibility to electrophiles.
  • Stability of Diazonium Salts: The basicity also plays a role in the stability and reactivity of the diazonium salts formed from phenylamine.

Conclusion

Understanding the reactions of phenylamine, including bromination, diazonium salt formation, and azo compound synthesis, is integral to mastering aromatic chemistry. These reactions are not only academically significant but also have vast industrial applications, particularly in dye synthesis. Mastery of these concepts is essential for students pursuing A-level Chemistry, providing a solid foundation for further study and application in organic chemistry.

FAQ

During the bromination of phenylamine, several safety precautions are essential due to the reactive nature of the chemicals involved. Firstly, the reaction should be conducted in a well-ventilated area or under a fume hood to avoid inhalation of bromine vapours, which are corrosive and harmful to the respiratory tract. Protective clothing, including gloves and goggles, should be worn to prevent skin and eye contact with bromine, as it can cause burns and irritation. Additionally, phenylamine is a toxic and potentially carcinogenic substance, so avoiding direct contact and inhalation is crucial. The reaction should be carried out with care to avoid spills and splashes, and all materials should be handled using appropriate equipment like tongs or tweezers. It's also important to be prepared for an accidental spill by having neutralizing agents, like sodium bisulfite solution, readily available. Following these safety measures is critical to prevent chemical accidents and ensure a safe laboratory environment.

Phenol is often chosen as the coupling partner for diazonium salts in the synthesis of azo dyes due to its reactivity and the properties of the resulting dye. Phenol, being an aromatic compound with an –OH group, is electron-rich, which makes it highly reactive towards electrophilic diazonium salts. The –OH group increases the electron density on the aromatic ring, particularly at the ortho and para positions, facilitating the electrophilic substitution reaction that forms the azo linkage. Moreover, the hydroxyl group in phenol can form hydrogen bonds, which enhance the solubility and stability of the resulting azo dye in various mediums. This is particularly advantageous in dye applications, as it improves the dye's adherence to fabrics and its overall durability. Additionally, the combination of phenol with diazonium salts can yield a wide range of colours, making it a versatile choice for dye synthesis.

The formation of diazonium salts from phenylamine is considered a key reaction in organic synthesis due to the versatility and reactivity of diazonium salts as intermediates. Diazonium salts, such as benzene diazonium chloride, can undergo a variety of reactions, enabling the synthesis of a wide range of organic compounds. They are particularly useful in creating complex molecules, including azo dyes, aromatic ethers, halogenated aromatics, and phenolic compounds. The diazonium group can be replaced with other functional groups through reactions like azo coupling, Sandmeyer reactions, and Schiemann reactions. This versatility makes diazonium salts valuable tools in synthetic organic chemistry, allowing chemists to construct complex molecules with precise control over the structure. Additionally, the conditions required for diazonium salt formation are relatively mild and the reactions are generally high-yielding, making this approach efficient and practical for both laboratory and industrial applications.


The synthesis of diazonium salts from phenylamine exemplifies the importance of temperature control in chemical reactions. Diazonium salts are generally unstable and can decompose to form hazardous compounds. To mitigate this risk and ensure the safe formation of these salts, the reaction is conducted at low temperatures, typically below 5°C. This low temperature is crucial for stabilizing the diazonium salt, preventing its decomposition. The reaction involves phenylamine reacting with nitrous acid, which is produced in situ from sodium nitrite and hydrochloric acid. If the temperature is not adequately controlled and exceeds the recommended range, the diazonium salt can decompose rapidly, leading to the formation of undesirable and potentially dangerous byproducts. This demonstrates the significance of temperature as a key variable in chemical synthesis, affecting both the yield and safety of the reaction.

The amino group in phenylamine plays a crucial role in electrophilic substitution reactions due to its electron-donating nature. When attached to a benzene ring, the amino group increases the electron density of the ring through resonance. This occurs as the lone pair of electrons on the nitrogen atom can partially delocalize into the aromatic system. This delocalization enhances the electron density, particularly at the ortho and para positions relative to the amino group, making these positions more reactive towards electrophiles. In electrophilic aromatic substitution reactions, such as bromination, these positions are preferentially attacked. The increased reactivity due to the amino group means that reactions can occur under milder conditions compared to benzene. Additionally, the ortho and para-directing nature of the amino group influences the regiochemistry of the reaction, determining the position at which electrophiles add to the aromatic ring.

Practice Questions

Explain the mechanism of the bromination of phenylamine and compare it to the bromination of benzene.

Phenylamine undergoes bromination more readily than benzene due to the electron-donating effect of the amino group. In phenylamine, the lone pair of electrons on the nitrogen atom delocalizes into the benzene ring, increasing the electron density, particularly at the ortho and para positions. This makes these positions more susceptible to electrophilic attack. The mechanism involves the initial formation of a bromonium ion, which then attacks the benzene ring, leading to the substitution of a hydrogen atom with a bromine atom. Unlike benzene, which requires a catalyst (like FeBr₃) for bromination, phenylamine does not need a catalyst due to its increased reactivity. The major product is 2,4,6-tribromophenylamine, with bromine substituents at the ortho and para positions relative to the amino group.

Describe the synthesis of azo dyes from phenylamine, detailing the conditions and the chemical reactions involved.

The synthesis of azo dyes from phenylamine involves two key steps: the formation of a diazonium salt and a subsequent coupling reaction with an aromatic compound like phenol. Initially, phenylamine is reacted with nitrous acid, prepared in situ from sodium nitrite and hydrochloric acid, under cold conditions (below 5°C) to form benzene diazonium chloride. This diazonium salt is then reacted with phenol in alkaline conditions to undergo a coupling reaction. The diazonium ion acts as an electrophile and attacks the electron-rich phenol, forming a stable azo linkage (N=N). The resulting compound is an azo dye, characterised by its vibrant colour and stability, making it suitable for use in textile dyeing. The overall process is an excellent example of electrophilic aromatic substitution and highlights the importance of reaction conditions in determining product formation.

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