Physical Sciences and Mathematics Commons^™

Synthesis Of Diaryl And Alkyl-Aryl Ethers Via Diaryl Iodonium Reagents, Rory Tennessee Gallagher

Dissertations and Theses

Substituted benzenoid rings are a prevalent motif in many industries including high tech, agrochemicals, and pharmaceuticals. As a result, the arylation of chemical compounds is a highly sought-after chemical transformation. There are many literature methods to achieve this chemical transformation, nucleophilic aromatic substitution and transition metal catalysis are both widely used and studied. Diaryliodonium salt mediated chemistry is an attractive alternative to these methods as it does not require the expensive toxic metals and designer ligands of transition metal catalysis and is not restricted to electron deficient aryl rings with specific substitution patterns like nucleophilic aromatic substitution.

Many diaryliodonium salt …

Speciation Of Diaryliodonium Salts In Solution And Their Reactivity Towards N-Nucleophiles (Phthalimide And Amines) And O-Nucleophiles (Phenols And Phenoxide), Souradeep Basu

Dissertations and Theses

Benzenoid rings are prevalent in pharmaceutical drug molecules, agrochemical molecules and even in some polymers used in electronic device. Aryl rings are often installed using metal catalysis, however, metal free arylations are known but limited. Diaryliodonium salts are novel electrophilic arylating agents. Herein, metal free N-arylation of phthalimide and diarylether formation using aryl(TMP)iodonium salts is described.

The structure of diaryliodonium salts has been primarily studied in either the solid state or in-silico. The structure and speciation of diaryliodonium salts in solution is not well explored. In this work evidence of dimer formation of aryl(Mes)iodonium salts in chloroform using …

The Preparation Of Diaryliodonium Salts For Application In Arylation Chemistry, Thomas Ludwig Seidl

Dissertations and Theses

Diaryliodonium salts offer potential as novel reagents for arylation chemistry. An overall goal and successful outcome of this work has been to further understanding of diaryliodonium salt chemistry by developing practical methods that enable chemists more convenient access to these reagents, for the purpose of reaction development. To this end a robust and convenient preparation method has been developed and resulted in novel commercially available diaryliodonium salts. The remainder of the work described, has focused on understanding the parameters important to diaryliodonium mediated arylation and has resulted in a solid framework that multiple future development efforts can build upon.

A …

The Discovery And Development Of Metal-Free Arylation Reactions With Unsymmetrical Diaryliodonium Salts, Sunil Kumar Sundalam

Dissertations and Theses

Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous amount of research has been published in achieving these chemical transformations using stoichiometric reagents and transition metal-catalyzed reactions. However, challenges still remain. An alternative and comparable methodology to metal-catalyzed reactions to overcome the drawbacks will advance this particular area of research is desirable.

Hypervalent iodine compounds offer a promising approach to metal-free arylation reactions. These mild, air and moisture stable compounds have showed significant success as non-toxic and metal-free reagents …

Synthesis And Characterization Of Novel Fluorine Containing Alkylsulfonyls And Sulfonates : Fluorinated Sulfonyl Methanes And Derivatives, Nelson R. Holcomb

Dissertations and Theses

A series of salts of the strong fluorocarbon acid bis(trifluoromethylsulfonyl)methane were made: (CF3S02 ) 2CHK, (CF3S02 ) 2CHLi, [ (CF3S02 ) 2CH] 2Ca, [ (CF3S02 ) 2CH] 2Hg, (CF3S02 ) 2CHAg, [ (CF3S02 ) 2CH] 3La. Their reactivity and use as organic intermediates were investigated. The salts were made from their corresponding carbonates, oxides, or hydrides. The reaction times for the salts is generally short, however the purification process was laborious, involving recrystallization from organic solvents and drying under vacuum. The lithium salt is being evaluated as a solid state battery electrolyte. Derivatives of bis(trifluoromethylsulfonyl)methane were made by using the …