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CIE A-Level Chemistry Study Notes

32.2.1 Production of Phenol from Phenylamine

Introduction

Phenol, an essential aromatic compound, plays a pivotal role in the chemical industry. Its synthesis from phenylamine demonstrates key concepts in organic chemistry, providing an excellent example of complex reaction mechanisms and chemical transformations.

Phenylamine to Diazonium Salt

Formation of Diazonium Salt

The conversion of phenylamine to phenol begins with the formation of a diazonium salt, a crucial intermediate in this synthesis.

Reactants and Conditions

  • Reactants: Phenylamine (C₆H₅NH₂) reacts with nitrous acid (HNO₂).
  • Catalyst: Hydrochloric acid (HCl) is used to generate nitrous acid in situ from sodium nitrite (NaNO₂).
  • Temperature: Maintained at 0-5°C to ensure stability of the diazonium ion.

Mechanism of Reaction

1. Formation of Nitrous Acid: Sodium nitrite reacts with HCl to form nitrous acid.

2. Nitrosation of Phenylamine: Phenylamine reacts with nitrous acid, leading to the diazonium ion (C₆H₅N₂⁺) and water.

Key Point: Temperature control is critical; higher temperatures can lead to decomposition of the diazonium ion.

Phenylamine (C₆H₅NH₂) reacts with nitrous acid (HNO₂) to form Diazonium Salt

Image courtesy of ChemistryStudent

Significance of the Diazonium Salt

Diazonium salts are versatile intermediates, enabling a variety of subsequent reactions, including the synthesis of aromatic compounds like phenol.

Conversion to Phenol

Hydrolysis of Diazonium Salt

The diazonium salt undergoes hydrolysis to form phenol, a critical step in the reaction sequence.

Reactants and Conditions

  • Reactant: Diazonium salt (C₆H₅N₂⁺Cl⁻).
  • Solvent: Water is used to facilitate the reaction.
  • Temperature: Slightly increased to about 10°C to promote hydrolysis.

Mechanism of Reaction

1. Hydrolysis Process: The diazonium group is replaced by a hydroxyl group, forming phenol.

2. Byproduct Formation: Nitrogen gas is released as a byproduct.

Key Point: The hydrolysis step requires precise temperature control for efficient conversion to phenol.

Hydrolysis of diazonium salt (C₆H₅N₂⁺Cl⁻) to form phenol

Image courtesy of Vedantu

Importance of the Hydrolysis Step

Hydrolysis of the diazonium salt is a prime example of how functional groups in organic compounds can be altered through specific reactions.

Analytical Monitoring of the Reaction

Techniques for Monitoring

Analytical methods are employed to ensure the accuracy and efficiency of the phenol production process.

Spectroscopic Methods

  • Infrared (IR) Spectroscopy: Used to identify functional groups present in the reactants and products.
  • Nuclear Magnetic Resonance (NMR) Spectroscopy: Provides detailed information about the molecular structure and the environment of individual atoms within the molecule.

Chromatographic Techniques

  • High-Performance Liquid Chromatography (HPLC): Employed to separate, identify, and quantify the components of the reaction mixture.

Key Point: These techniques are vital for quality control, ensuring the desired product is obtained with high purity.

Safety and Environmental Aspects

Chemical Handling and Safety

  • Phenylamine: Handling requires precautions due to its toxic nature.
  • Nitrous Acid and Diazonium Salts: These compounds can be explosive, especially at elevated temperatures, necessitating careful handling.

Environmental Impact and Disposal

  • Waste Management: Proper disposal methods are crucial to mitigate environmental harm.
  • Regulatory Standards: Compliance with safety and environmental regulations is essential in chemical synthesis.

Key Point: Maintaining safety in the laboratory and responsible environmental practices are integral parts of chemical synthesis processes.

Phenol (C₆H₅OH) in lab

Image courtesy of luchschenF

Educational Significance

Key Learning Outcomes

The synthesis of phenol from phenylamine serves as an educational tool, providing insights into:

  • Nucleophilic Substitution Reactions: It illustrates the conversion of an amine group to a hydroxyl group, a common reaction in organic chemistry.
  • Understanding Reaction Mechanisms: The process exemplifies how various conditions influence the course of a chemical reaction.
  • Development of Analytical Skills: Students learn to apply spectroscopic and chromatographic methods to monitor and verify the progress and success of chemical reactions.

Key Point: This synthesis not only demonstrates important chemical principles but also enhances students' understanding of practical applications in organic chemistry.

In summary, the production of phenol from phenylamine offers a comprehensive look at a significant chemical process. It encompasses various aspects of organic chemistry, from reaction mechanisms and chemical transformations to analytical techniques and safety considerations. This synthesis process is not only crucial for industrial applications but also serves as an invaluable learning experience for students, showcasing the depth and breadth of organic chemistry.

FAQ

Yes, the diazonium salt formed from phenylamine can be used to synthesise a variety of other compounds besides phenol, highlighting its versatility as an intermediate in organic chemistry. Diazonium salts are particularly useful in the synthesis of azo dyes, where they react with aromatic compounds to form brightly coloured azo compounds. This reaction is commonly used in the dyeing of textiles and the production of pigments. Additionally, diazonium salts can undergo Sandmeyer reactions, where they are transformed into chlorobenzene, bromobenzene, or iodobenzene through reactions with copper(I) chloride, bromide, or iodide, respectively. They can also react with copper(I) cyanide to form benzonitrile. Furthermore, diazonium salts can participate in the Schiemann reaction to produce fluorobenzene. These reactions demonstrate the broad utility of diazonium salts in organic synthesis, enabling the production of a wide range of aromatic compounds with various functional groups.

Handling diazonium salts in the laboratory requires stringent safety precautions due to their potentially explosive nature and toxicity. Firstly, it is crucial to always prepare and use diazonium salts in cold conditions, typically below 5°C, to prevent their decomposition and the potential for an explosive reaction. Personal protective equipment (PPE), including lab coats, gloves, and safety goggles, should be worn at all times to avoid skin contact and protect the eyes. Work in a well-ventilated area or under a fume hood to avoid inhalation of any vapours or dust. Diazonium salts should be prepared in small quantities to minimise the risk, and they should never be dried, as dry diazonium salts are significantly more sensitive and prone to detonation. Any waste containing diazonium salts should be disposed of properly according to laboratory safety protocols and environmental regulations. Understanding and adhering to these safety measures are essential to prevent accidents and ensure a safe laboratory environment.


The hydrolysis of the diazonium salt is preferred for the production of phenol over direct functionalisation of benzene due to several reasons related to efficiency, selectivity, and safety. Direct functionalisation of benzene to introduce a hydroxyl group requires harsh conditions, such as the use of strong acids like sulfuric acid under high temperatures. This method, often involving electrophilic aromatic substitution, can lead to a mixture of products and requires extensive purification steps. In contrast, the diazonium salt route offers a more controlled and specific pathway to phenol. The formation of the diazonium salt from phenylamine is relatively straightforward, and its subsequent hydrolysis to phenol occurs under milder conditions with higher selectivity and yield. This method also avoids the use of strong acids and high temperatures, making it safer and more environmentally friendly. Additionally, the intermediate diazonium salt can be used to synthesise other aromatic compounds, providing versatility in chemical synthesis.

The presence of the hydroxyl group in phenol significantly affects its physical properties compared to benzene. Firstly, the hydroxyl group is a polar functional group, which increases the polarity of phenol relative to benzene. This polarity contributes to stronger intermolecular forces, specifically hydrogen bonding, between phenol molecules. As a result, phenol has a higher melting and boiling point than benzene. Phenol is solid at room temperature, whereas benzene is a liquid. Additionally, the hydroxyl group increases the solubility of phenol in water. While benzene is hydrophobic and poorly soluble in water, phenol can form hydrogen bonds with water molecules, enhancing its solubility. This difference in solubility is particularly significant in biological and environmental contexts, where phenol's water solubility can impact its distribution and effects.

Using cold conditions, typically 0-5°C, during the formation of the diazonium salt from phenylamine is crucial to prevent the decomposition of the diazonium ion. Diazonium ions are generally unstable and can decompose rapidly at higher temperatures, leading to the release of nitrogen gas and the formation of unwanted by-products. The low temperature slows down the molecular movements, thus stabilising the diazonium ion and preventing its premature breakdown. This stability is essential for the diazonium ion to undergo the subsequent hydrolysis step efficiently. Moreover, keeping the reaction mixture cold minimises the risk of side reactions, which could otherwise lead to a decrease in the yield and purity of the desired phenol product. It's a critical parameter to control in order to achieve a successful and controlled synthesis of phenol from phenylamine.

Practice Questions

Describe the process of converting phenylamine to phenol, including the conditions required for the formation of diazonium salt and its subsequent hydrolysis. Explain the significance of maintaining specific temperature conditions throughout the process.

The conversion of phenylamine to phenol involves two main steps: the formation of a diazonium salt and its hydrolysis. Initially, phenylamine reacts with nitrous acid, formed in situ from sodium nitrite and hydrochloric acid, to produce a diazonium salt. This reaction requires a temperature of 0-5°C to stabilise the diazonium ion and prevent its decomposition. In the second step, the diazonium salt undergoes hydrolysis, where the diazonium group is replaced by a hydroxyl group, forming phenol. This step is conducted at a slightly elevated temperature, around 10°C, to facilitate hydrolysis while avoiding side reactions. The strict temperature control is crucial in both steps to ensure the stability of the diazonium ion and the efficiency of the hydrolysis process, leading to the successful production of phenol.

In the synthesis of phenol from phenylamine, explain why specific analytical techniques such as Infrared (IR) Spectroscopy and High-Performance Liquid Chromatography (HPLC) are used. Discuss their importance in monitoring the reaction process.

Infrared (IR) Spectroscopy and High-Performance Liquid Chromatography (HPLC) are essential analytical techniques used in the synthesis of phenol from phenylamine to ensure the accuracy and purity of the product. IR Spectroscopy is employed to identify functional groups in the reactants and products by their characteristic vibrations. This technique helps in confirming the presence of the hydroxyl group in phenol and ensuring the complete conversion of the diazonium salt. HPLC is utilised to separate, identify, and quantify the components of the reaction mixture. It is particularly important in monitoring the purity of phenol and detecting any impurities or by-products. These analytical methods are crucial in maintaining the quality of the final product, ensuring that the reaction proceeds as expected, and verifying the success of the synthesis process.

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