Date of Award

12-2010

Document Type

Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Carl LeBlond, Ph. D.

Second Advisor

Keith Kyler, Ph. D.

Third Advisor

Jonathan Southard, Ph. D.

Fourth Advisor

Justin Fair, Ph. D.

Abstract

Iodohydrins are important intermediates in the synthesis of pharmaceuticals and other specialty chemicals. Traditional methods of iodohydroxylation are costly or create large amounts of organic waste. Herein, we report the development of a novel method for the synthesis of iodohydrins from common household bleach rather than the current method of using the more costly N-chlorosuccinimide (NCS). In the new method hypoiodous acid is generated in-situ from NaOCl (bleach) and NaI. The Cl- ion was introduced through bleach and chloride generated in the system during the formation of the hypoiodous acid. The pH is controlled with a 2M borate buffer system with pH of 8 rather than on demand addition of H2SO4. It has been shown that this procedure can be adopted for a variety of alkenes. The highest yields were obtained for a NaOCl: NaI ratio of 2:1.8. The products obtained were in substantial yield with the highest of 72% for styrene. Epoxidation of the iodohydrins indicated the formation of byproducts in which the hydroxyl group in the iodohydrin is replaced by a chloride to form 2-chloro-1-iodo product. The formation of byproduct is possibly due to a competition between chloride ion, Cl-, and hypoiodous acid during the attack the iodonium intermediate.

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