Chemistry of Pentafluorothio (SF5) Alkyl Derivatives

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Chemistry of Pentafluorothio (SF5) Alkyl Derivatives

Transcript Of Chemistry of Pentafluorothio (SF5) Alkyl Derivatives

Portland State University
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Dissertations and Theses

Dissertations and Theses

1990
Chemistry of Pentafluorothio (SF5) Alkyl Derivatives
Rolf Walter Winter Portland State University

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Recommended Citation Winter, Rolf Walter, "Chemistry of Pentafluorothio (SF5) Alkyl Derivatives" (1990). Dissertations and Theses. Paper 1281. https://doi.org/10.15760/etd.1280
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CHEMISTRY OF PENTAFLUOROTHIO (SF5) ALKYL DERIVATIVES
by ROLF WALTER WINTER
A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in
ENVIRONMENTAL SCIENCES AND RESOURCES/CHEMISTRY
Portland State University 1990

TO THE OFFICE OF GRADUATE STUDIES: The members of the Committee approve the dissertation
of Rolf winter presented October 4, 1990.

APPROVED:
Pavel K. Smej Resources Ph.D.
C. William Savery, and Research

1 Sciences and Provost for Graduate Studies

AN ABSTRACT OF THE DISSERTATION OF ROLF WALTER WINTER FOR THE DOCTOR OF PHILOSOPHY in Environmental Sciences and Resources/Chemistry presented October 4, 1990.

Title:

Chemistry of Pentafluorothio (SF5) Alkyl Derivatives.

APPROVED BY MEMBERS OF THE DISSERTATION COMMITTEE:

This thesis is divided into four parts: Part I describes the preparation of a number of useful
intermediates from the suItone F5SCHCF20S02' OJ . These
intermediates include the following: the ketene

2

(.£1) ,

and various ionic intermediates of the form y+

[F5SC(S02F)COX]-

These intermediates play an important

role in providing new pathways for preparing fluorosulfonic

acid precursors. Fluorosulfonic acids are excellent

candidates to improve the efficiency of environmentally safe

fuel cells. It was possible to obtain new derivatives of ~
by various reactions of 21, .£1 and the ionic intermediates,

but it was not possible to introduce an alkyl sUbstituent

with either of the intermediates.

Part II is concerned with the synthesis of SF5

containing epoxides as possible monomers. When polymerized,

materials of high dielectric strength and high chemical

resistance should be obtained. The reaction chemistry of one

of the epoxides was investigated and it was found that all

reactions studied were accompanied by the loss of the SF5

group. Thus, it was not possible to obtain any polymeric

materials.

Part III deals with the synthetic accessibility of SF5

malonic esters and thence of SF5 acrylic esters. These

compounds should serve as building blocks in the synthesis

of SF5 containing pyrimidines. The CF3 analogue, 5-

trifluoromethyl uracil, is used as an antiviral drug. In

order to synthesize either SF5 malonic ester or 2-SF5

acrylic ester an SF5 group has to be introduced at a

secondary carbon. A secondary SF5 compound could be

3
synthesized (F5SCH(COOC2H5) (CHBrOAc)) but could not be converted to the respective malonic ester F5SCH (COOC2H5)2. compound.
Part IV describes the reactions and preparations of part I-III.

To My Family

ACKNOWLEDGEMENT
I would like to thank Professor Gard for his support and kindness in the course of this work. I am grateful to the bright stars on their celestial path that guided me in the years past towards Arcadia.

TABLE OF CONTENTS PAGE
DEDICATION ......................•......•............... iii ACKNOWLEDGEMENT . . . . . . . . . . . . . . . . • . . . . • • . . . • . . . . . . . . . . . . . . i v LIST OF TABLES •..............••..•.•.................. viii LIST OF FIGURES ............•.....•...•.................. ix
CHAPTER PART I: DERIVITIZATIONS OF F5SCHCF20S02
I INTRODUCTION ...............•..•.......•............ 2 II SIGNIFICANCE AND ENVIRONMENTAL RELATIONSHIP ...••..• 4 III GENERAL DISCUSSION, DERIVITIZATION OF F5SCHCF20S02.9 IV RESULTS AND DISCUSSION .....•.........••........... 21
Synthesis and Reactions of SF5C(S02F)=C=O ..... 21 The Formal Addition of RO- to SF5C(S02F)=C=Oi Synthesis and Reactions of F5SC-(S02F)COOR .... 35 Properties of Cs+ [SF5C(S02F)COF]- ............ 43 Synthesis and Properties of F4S=CCF20S02 ...... 51 The Conversion of an SF5 Group into an (F2S=O)= Group ......................................... 59 Nuclear Magnetic Resonance Spectra ............ 63 Features of X-Ray Structures .................. 74 V SUNTHESIS OF PENTAFLUOROSULFUR BROMIDE, SF5BR ..... 83
VI CONCLUSION . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . 87

vi PART II: SYNTHESIS AND REACTIONS OF SF5-EPOXIDES
I INTRODUCTION ...................................... 89 II RESULTS AND DISCUSSION ............................ 95 III REACTIONS OF F5SCFCF26 ........................... 100
Synth~sis of the Starting Olefins . . . . . . . . . . . . l05 IV INFRARED, 19F AND 13 C N.M.R. SPECTRA ............. 107
V CONCLUSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

PART III: TOWARDS THE SUNTHESIS OF PENTAFLUOROTHIO MALONIC ACID
I INTRODUCTION ..................................... 112 II A GENERAL OUTLINE FOR THE SYNTHESIS OF SF5 COMPOUNDS
................................................ . 115
III RESULTS AND DISCUSSION AND THE SYNTHESIS OF SF5CH(COOC2H5)CHBROCOCH3·························119
IV THE X-RAY STRUCTURE OF (F5SCH2CHO)3 .............. 133
V CONCLUSION . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . 136

PART IV: EXPERIMENTAL PART I GENERAL METHODS .................................. 138
II PREPARATIONS AND REACTIONS ....................... 140

REFERENCES

I

••••••.•••••••••••••••••••••••••••••••••••••••••• 240

II ................................................. 247

III ................................................. 250
ReactionsIntermediatesPentafluorothioSynthesisDissertation