Doctoral Dissertations
Abstract
"Organofluorine chemistry plays a critical role in synthetic chemistry due to the unique properties of fluorine. However, the S-trifluoromethylation of thiols remains underexplored, with existing methods often relying on toxic and expensive organometallic catalysts. Given the advantages of S-trifluoromethylated compounds, including enhanced pharmacological activity and improved metabolic stability, we developed a green and cost-effective method for the synthesis of S-CF3 compounds using diacetyl as the organic catalyst and Langloi's reagent as the trifluoromethylating reagent. This reaction, which proceeds under mild conditions using visible light photoredox catalysis, works across various substrate scopes, including aromatic, heteroaromatic, and aliphatic thiols.
Chemical Warfare Agents (CWAs) are highly toxic substances used in terrorist attacks. Due to their lethal nature, their rapid and effective decontamination is critical to human and environmental health. In this study, we investigated the efficiency of various azoles: imidazole, benzothiazole, mercaptobenzothiazole, mercaptobenzimidazole, mercaptobenzoxazole, S-methylbenzothiazole, and S-methylbenzimidazole in degrading dimethyl chlorophosphate (DMCP)—nerve agent simulant—via hydrolysis in borate buffer at pH 8 and 9. Mercaptobenzothiazole and mercaptobenzoxazole demonstrated rapid hydrolysis of DMCP to dimethyl phosphate (DMP) and monomethyl phosphate (MMP) within 3 minutes at pH 9. This study demonstrates the potential of small molecules to effectively decontaminate nerve agent simulants, typically achieved with more complex materials"-- Abstract, p. iv
Advisor(s)
Sotiriou-Leventis, Lia
Committee Member(s)
Choudhury, Amitava
Alajo, Ayodeji Babatund
Woelk, Klaus
Eze, Michael
Department(s)
Chemistry
Degree Name
Ph. D. in Chemistry
Publisher
Missouri University of Science and Technology
Publication Date
Spring 2025
Pagination
xii, 117 pages
Note about bibliography
Includes_bibliographical_references_(pages 67, 104 and 108-116)
Rights
©2024 Raheemat Rafiu , All Rights Reserved
Document Type
Dissertation - Open Access
File Type
text
Language
English
Thesis Number
T 12471
Recommended Citation
Rafiu, Raheemat, "Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols And Investigation Of Ph-Dependent Decontamination Of Dimethyl Chlorophosphate, A Nerve Agent Simulant, Via Hydrolysis With Azoles" (2025). Doctoral Dissertations. 3376.
https://scholarsmine.mst.edu/doctoral_dissertations/3376
