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Browsing by Subject "Hypervalent"

Now showing 1 - 3 of 3
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    Preparation, Structure, and Reactivity of the First Bicyclic Benziodazole and its Monocyclic Analogue
    (2019-08) Shea, Michael
    Nitrogen containing mono-heterocyclic hypervalent iodine(III) compounds, benziodazoles, have been investigated by several research groups as well as ours. These compounds are commonly used as efficient oxidative reagents for various organic substrates. The preparation, structure, and reactivity of the first bicyclic benziodazole compound, N,N’-diisopropylbenziodazole, will be reported and compared to the monocyclic N-isopropyl-m-chlorobenzoate benziodazole. Both benziodazoles were prepared by the m-chloroperoxybenzoic acid oxidation of 2-iodo-N-isopropylbenzamide or 2-iodo-N,N'-diisiopropylisophthalamide, respectively, and their structures were established by X-ray crystallography. These benziodazoles were investigated as efficient reagents for oxidatively assisted coupling reactions to form esters and amides.
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    Recyclable reagents and Catalytic systems based on hypervalent iodine Chemistry
    (2013-07) Middleton, Kyle Richard
    Hofmann rearrangement of carboxamides to carbamates using Oxone® as an oxidant can be efficiently catalyzed by iodobenzene. This reaction involves hypervalent Iodine species generated in situ from catalytic amounts of PhI and Oxone® in the presence of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) in aqueous methanol solutions. Under these conditions, Hofmann rearrangement of various carboxamides affords the corresponding carbamates in high yields. Aziridination of alkenes to aziridines using catalytic amounts of tetrabutylammonium iodide, meta-Chloroperoxybenzoic acid (mCPBA) and PhthNH2 can be run under metal-free conditions. This reaction involves an oxidized iodine species generated in situ from Bu4NI and mCPBA. Under optimized conditions, Conversion of various alkenes to the corresponding aziridine products proceeds in comparable yields to previous by reported procedures. A green, recyclable and efficient catalytic oxidative system based on SiO2-supported RuCl3 and 3-(dichloroiodo)benzoic acid for the oxidation of alcohols and sulfides in water is developed. This catalytic oxidative system effects clean and efficient oxidation of a wide range of alcohols to the corresponding aldehydes and ketones, or sulfides to sulfoxides in high conversions with excellent chemoselectivity, under mild conditions. Furthermore, the SiO2-RuCl3 catalyst can be recovered by simple filtration and recycled in up to six consecutive runs without significant loss of activity. The reduced form of 3-(dichloroiodo)benzoic acid, 3-iodobenzoic acid, can be easily separated from reaction mixtures and converted back to 3-(dichloroiodo)benzoic acid by treatment with NaOCl and aqueous HCl in about 90% overall yield.
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    Synthesis and Reactivity of Vinyl Iodonium Salts
    (2016) Liebl, Mackenzie
    In Dr. Zhdankin’s research lab, one of our main focuses is on the chemistry of iodine. Iodine is the largest nonradioactive nonmetal on the planet and it is environmentally friendly, commercially available and safe to work with. It is also has a special ability to exceed its octet of electrons and become hypervalent due to its large size. This ability to become hypervalent is typically only exhibited by transition metals which are commonly used in many different chemical reactions to make pharmaceuticals, agriculture chemicals, and many other useful products. Transition metals, however, tend to be expensive, environmentally toxic and can be unsafe to work with in a lab setting due to their toxic properties. Therefore, it would be useful to find an alternative to transition metals to synthesize these useful products; this is where iodine comes in. Since it is able to exhibit the same hypervalent property as transition metals, it offers an advantage since it is nontoxic and cheap. It is for this reason that research on hypervalent iodine compounds is so important for medicine, agriculture, and our overall understanding of chemistry.