Question

A reaction for converting ketones to lactones, called the Baeyer-Villiger reaction, is used in the manufacture of plastics and pharmaceuticals. 3 Chloroperbenzoic acid is shock-sensitive, however, and prone to explode. Also, 3 -chlorobenzoic acid is a waste product. An alternative process being developed uses hydrogen peroxide and a catalyst consisting of tin deposited within a solid support. The catalyst is readily recovered from the reaction mixture. (a) What would you expect to be the other product of oxidation of the ketone to lactone by hydrogen peroxide? (b) What principles of green chemistry are addressed by use of the proposed process?

Short answer

(a) The other product of oxidation of the ketone to lactone by hydrogen peroxide is water (H2O). (b) The proposed process addresses the following principles of green chemistry: Prevention, Safer Solvents and Auxiliaries, Catalysis, and Inherently Safer Chemistry for Accident Prevention. This makes it a more environmentally friendly and safer method for converting ketones to lactones.

Step-by-step solution

a) Determining the other product of oxidation with hydrogen peroxide

To determine the other product resulting from the oxidation of the ketone to lactone with hydrogen peroxide, analyze the available reactants and products. The reaction can be represented as: Ketone + Hydrogen Peroxide → Lactone + Other Product Given that hydrogen peroxide (H2O2) donates an oxygen atom for oxidation, one can conclude that a water molecule (H2O) will likely form as a byproduct in this specific oxidative reaction: Ketone + H2O2 → Lactone + H2O Thus, the other product of the oxidation of the ketone to lactone by hydrogen peroxide is water (H2O).

b) Principles of green chemistry addressed by the proposed process

Green chemistry focuses on designing products and processes that minimize the use and generation of hazardous substances. The principles of green chemistry being addressed by using hydrogen peroxide and a tin catalyst deposited within a solid support are as follows: 1. Prevention: The proposed process avoids the use of hazardous chemicals, like shock-sensitive 3-chloroperbenzoic acid, preventing the creation of harmful waste and reducing the risk of explosion. 2. Safer Solvents and Auxiliaries: The replacement of 3-chloroperbenzoic acid with hydrogen peroxide makes the overall reaction safer, as hydrogen peroxide is a less hazardous chemical. 3. Catalysis: The use of a tin catalyst deposited within a solid support increases the efficiency of the reaction. Catalysts ultimately reduce the energy consumption and waste generation, as they generally increase the rate of the reaction and may be reusable. 4. Inherently Safer Chemistry for Accident Prevention: Reducing the use of shock-sensitive and explosive chemicals like 3-chloroperbenzoic acid helps minimize the risk of accidents. Hydrogen peroxide is inherently safer in this context. Based on the analysis above, the proposed process with hydrogen peroxide and a tin catalyst addresses multiple green chemistry principles, making it a more environmentally friendly and safer method for converting ketones to lactones.

Key concepts

Ketone Oxidation

Ketone oxidation is a chemical process where a ketone molecule gains an additional oxygen atom, transforming into another compound. In the Baeyer-Villiger reaction, ketones are oxidized into lactones. This transformation is crucial in the manufacture of various products, such as pharmaceuticals and plastics.

The reaction involves the conversion of a ketone to a lactone using an oxidizing agent. In the example discussed, hydrogen peroxide serves as this agent. During the process, hydrogen peroxide donates an oxygen atom to the carbonyl group of the ketone. As a result, the ketone becomes a lactone and an additional byproduct, usually water, is produced.

Understanding ketone oxidation is essential for those in fields such as organic chemistry and material science, as it is a fundamental reaction that opens pathways for creating complex molecules through relatively simple transformations.

Green Chemistry

Green chemistry is all about designing chemical processes and products that reduce or eliminate the use and generation of hazardous substances. This concept ensures that chemical synthesis is safer, more environmentally friendly, and sustainable.

The goal is to:

• Prevent waste rather than treat or clean up waste after it's formed.
• Reduce energy use and increase efficiency.
• Use renewable resources whenever possible.
• Design chemicals and products that degrade into harmless products after use.

In the case of the Baeyer-Villiger reaction using hydrogen peroxide, several green chemistry principles are met. By replacing 3-chloroperbenzoic acid with hydrogen peroxide, the process becomes more eco-friendly and safe, adhering to the principle of having safer chemicals. This transformation aligns with the idea of preventing waste and making chemistry inherently safer.

Environmentally Friendly Catalysis

Environmentally friendly catalysis is about using catalysts that are safe for both the environment and human health. A catalyst is a substance that speeds up a chemical reaction but remains unchanged by the reaction. In more sustainable practices, catalysts can be recycled and reused, minimizing waste.

In the proposed process of using a tin catalyst within a solid support, environmental benefits are numerous:

• The catalyst is selective, meaning fewer byproducts and less waste.
• It reduces the need for excessive amounts of reactants, thereby conserving resources.
• Solvents and conditions are often milder, reducing the energy footprint of the reaction.

Implementing this type of catalysis not only streamlines the conversion from ketones to lactones but also ensures that the process leaves a lighter environmental mark. This showcases the potential for combining efficient chemical reactions with responsible environmental stewardship.

Hydrogen Peroxide Oxidation

Hydrogen peroxide oxidation is a chemical process where hydrogen peroxide acts as an oxidizing agent. It is a clean and efficient way to introduce oxygen into organic molecules. In the context of the Baeyer-Villiger reaction, hydrogen peroxide helps convert ketones into lactones.

This process is valuable because:

• Hydrogen peroxide is a relatively safe and eco-friendly oxidizer compared to traditional reagents.
• It often leads to fewer unwanted byproducts, making separation and purification easier.
• The byproduct, water, is benign and non-polluting.

Hydrogen peroxide's use highlights the principles of green chemistry by offering a less hazardous means of oxidation. Additionally, its utility in various industrial processes makes it an indispensable tool for achieving chemical transformations with a reduced environmental impact.