Table of contents

1. A Review of General Chemistry5h 5m
2. Molecular Representations1h 14m
3. Acids and Bases2h 46m
4. Alkanes and Cycloalkanes4h 17m
5. Chirality3h 39m
6. Thermodynamics and Kinetics1h 22m
7. Substitution Reactions1h 48m
8. Elimination Reactions2h 30m
9. Alkenes and Alkynes2h 9m
10. Addition Reactions3h 19m
11. Radical Reactions1h 58m
12. Alcohols, Ethers, Epoxides and Thiols2h 42m
13. Alcohols and Carbonyl Compounds2h 17m
14. Synthetic Techniques1h 26m
15. Analytical Techniques:IR, NMR, Mass Spect7h 3m
16. Conjugated Systems6h 13m
17. Ultraviolet Spectroscopy51m
18. Aromaticity2h 34m
19. Reactions of Aromatics: EAS and Beyond5h 1m
20. Phenols55m
21. Aldehydes and Ketones: Nucleophilic Addition4h 56m
22. Carboxylic Acid Derivatives: NAS2h 51m
23. The Chemistry of Thioesters, Phophate Ester and Phosphate Anhydrides1h 10m
24. Enolate Chemistry: Reactions at the Alpha-Carbon1h 53m
25. Condensation Chemistry2h 9m
26. Amines1h 43m
27. Heterocycles2h 0m
28. Carbohydrates5h 53m
29. Amino Acids4h 20m
30. Peptides and Proteins2h 42m
31. Catalysis in Organic Reactions1h 30m
32. Lipids 2h 50m
33. The Organic Chemistry of Metabolic Pathways2h 52m
34. Nucleic Acids1h 32m
35. Transition Metals6h 14m
36. Synthetic Polymers1h 49m

12. Alcohols, Ethers, Epoxides and Thiols

Sulfide Oxidation

Organic Chemistry

12. Alcohols, Ethers, Epoxides and Thiols

Sulfide Oxidation

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3:20 minutes

Problem 18

Textbook Question

Mustard gas, Cl–CH₂CH₂–S–CH₂CH₂–Cl, was used as a poisonous chemical agent in World War I. Mustard gas is much more toxic than a typical primary alkyl chloride. Its toxicity stems from its ability to alkylate amino groups on important metabolic enzymes, rendering the enzymes inactive.
a. Propose a mechanism to explain why mustard gas is an exceptionally potent alkylating agent.
b. Bleach (sodium hypochlorite, NaOCl, a strong oxidizing agent) neutralizes and inactivates mustard gas. Bleach is also effective on organic stains because it oxidizes colored compounds to colorless compounds. Propose products that might be formed by the reaction of mustard gas with bleach.

Verified step by step guidance

Step 1: Analyze the structure of mustard gas (Cl-CH₂CH₂-S-CH₂CH₂-Cl). Note that it contains two alkyl chloride groups and a sulfur atom in the center, which can act as a nucleophile. The sulfur atom's lone pair can initiate an intramolecular reaction, forming a three-membered episulfonium ion intermediate.

Step 2: Propose the mechanism for mustard gas's alkylating ability. The sulfur atom attacks one of the carbon atoms bonded to a chlorine atom, displacing the chloride ion and forming the episulfonium ion. This intermediate is highly reactive and can easily react with nucleophiles, such as amino groups on enzymes, leading to alkylation and enzyme inactivation.

Step 3: Consider the reaction of mustard gas with bleach (NaOCl). Bleach is a strong oxidizing agent and can oxidize the sulfur atom in mustard gas. This oxidation likely converts the sulfur atom into a sulfoxide (R-S(=O)-R') or sulfone (R-S(=O)₂-R'), which are less reactive and no longer capable of forming the episulfonium ion.

Step 4: Propose the products of the reaction between mustard gas and bleach. The oxidation of the sulfur atom disrupts the ability of mustard gas to form the episulfonium ion, rendering it non-toxic. The products might include oxidized sulfur compounds such as sulfoxides or sulfones, along with chloride ions (Cl⁻) released during the reaction.

Step 5: Summarize the neutralization process. The reaction with bleach effectively inactivates mustard gas by oxidizing the sulfur atom, preventing the formation of the reactive episulfonium ion. This mechanism explains why bleach is effective in neutralizing mustard gas and highlights its utility as a decontaminant.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Alkylation Mechanism

Alkylation is a chemical process where an alkyl group is transferred to a nucleophile, such as an amino group in proteins. In the case of mustard gas, its structure allows it to undergo a nucleophilic substitution reaction, where the chlorine atoms are displaced, leading to the formation of a highly reactive sulfonium ion. This ion can then react with amino groups, resulting in the modification and inactivation of essential enzymes, which contributes to the toxicity of mustard gas.

Oxidizing Agents

An oxidizing agent is a substance that can accept electrons from another species, causing the oxidation of that species. In the context of bleach (sodium hypochlorite), it acts as a strong oxidizer that can react with mustard gas, breaking its chemical bonds and leading to the formation of less harmful products. This reaction is crucial for neutralizing the toxic effects of mustard gas and is also the basis for bleach's effectiveness in removing organic stains.

Chemical Reactivity of Mustard Gas

Mustard gas exhibits unique chemical reactivity due to its bifunctional nature, containing two reactive chlorine atoms. This allows it to form cross-links with biological macromolecules, such as DNA and proteins, leading to significant cellular damage. Understanding this reactivity is essential for predicting the products formed when mustard gas interacts with other chemicals, such as bleach, which can facilitate the breakdown of its toxic structure.

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