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Functionalization of fluorocarbons.

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Call No.	Ph.D. 2004
Author	Chen, Xudong.
Title	Functionalization of fluorocarbons.
Date	2004
Abstract	The great strength of the C-F bond has enabled fluorocarbons to find many industrial and domestic applications, and makes C-F activation a chemical and technical challenge akin to that of C-H bond activation in hydrocarbons. In our mission to tackle this problem, we first developed a low cost thermal reaction to reduce perfluoroalkanes with tertiary carbon centers selectively. Very strong reducing agents usually result in wholesale defluorination. Stopping at the partial reduction stage is difficult because the partially reduced species tend to be more reactive than the starting material. Our key to success is the use of hydroxide to trap intermediate species, which both introduces enolate functionality and avoids over-reduction at the same time. During this study, a surprising result led us to the investigation of a novel perfluoroallylic anion, formed by reduction of perfluoro-1,3-dimethylcyclohexane. Properly prepared, our perfluoro-1,3-dimethylcyclohex-2-enyl anion is stable, and its ring inversion barrier was determined by low-temperature NMR to be ΔH [double dagger] = 8.84 ± 0.14 kcal mol -1 and ΔS [double dagger] = 0.8 ± 0.6 cal mol -1 K -1. The acidity of its conjugate acid was determined to be ∼50 times greater in acetonitrile than that of 2,6-dinitro- p -cresol (p K a in water, 4.23). Working on esters of perfluorinated acids, another class of widely available and useful fluorocarbon derivatives, we invented a photoinduced iododefluorination reaction. The resulting α-iodoperfluoroacid esters are versatile reagents, undergoing various synthetically useful transformations. For example, we synthesized fluorotrifluoromethylketene adducts with styrene and benzaldehyde via α-iodoperfluoropropionic acid chloride. Synthesis of β-hydroxyesters was accomplished by Reformatsky reaction of an α-iodoperfluoroacid ester and benzaldehyde. An α,β-unsaturated perfluoroacid ester and an α-hydroperfluoroacid ester were also synthesized starting from an α-iodoperfluoroacid ester. One of our initial research goals was to introduce functionality onto Teflon ® surfaces at specific sites, in order to modify its surface properties. We applied the selective reduction to Teflon FEP ® , and preliminary results are promising. The IR spectrum of treated Teflon ® powder showed that the desired reaction happened on the surface, and the wettability of Teflon ® film was significantly improved in this way. Coordination of metal to the surface β-diketonate groups is still under investigation.
Description	xii, 151 leaves : ill. 28 cm.
Format	application/pdf
Advisor	David M. Lemal.
Subject	Fluorocarbons -- Synthesis. Fluorocarbons -- Derivatives. Activation (Chemistry). Polytef -- Surfaces. Organofluorine compounds -- Synthesis.
College	Dartmouth College -- Department of Chemistry.
Issuing Body	Dartmouth Dissertations are made available through the Dartmouth Digital Library.
Degree	Thesis (Ph.D.)--Dartmouth College.
Copyright	All rights reserved. No part of this book may be reproduced in any form by any electronic or mechanical means without permission in writing from the author.
DOI	http://dx.doi.org/10.1349/ddlp.39

Title	Page 1
Format	application/pdf
Issuing Body	Dartmouth Dissertations are made available through the Dartmouth Digital Library.
Degree	Thesis (Ph.D.)--Dartmouth College.
Full Text	Functionalization of Fluorocarbons A Thesis Submitted to the Faculty in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by Xudong Chen DARTMOUTH COLLEGE Hanover, New Hampshire June, 2004 Examining Committee ____________________________ (chair) Prof. David M. Lemal ____________________________ Prof. Gordon W. Gribble ____________________________ Prof. Jane E. G. Lipson ____________________________ Prof. Paul M. Lahti ____________________________ Carol L. Folt Dean of Graduate Studies

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Functionalization of fluorocarbons.

Functionalization of fluorocarbons.