hydrogen peroxide disproportionation and organic compound

184 Pages·2005·1.05 MB·English

HYDROGEN PEROXIDE DISPROPORTIONATION AND ORGANIC COMPOUND
OXIDATION BY PEROXYCARBONATE CATALYZED BY MANGANESE(II):
KINETICS AND MECHANISM

By

ANDREW P. BURKE

A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

2005
Copyright 2005

by

ANDREW P. BURKE
to my wife and parents
ACKNOWLEDGMENTS
The work presented here would not have been possible without the help and
support of a number of people. I would like to acknowledge these people individually for
their contributions in making the following document possible.
First, I would like to thank my advisor, Dr. David Richardson, for all of his help
and support during these past five years. Dr. Richardson has helped to make me a better
scientist. My presentation and writing skills have vastly improved under his advisement,
and they will prove useful in all my future endeavors. I have also had the opportunity to
learn from Dr. Richardson the proper method for performing chemical kinetics.
I would also like to thank the members of the Richardson group, both past and
present, for all of their help during the years. Without the fun environment they created,
working in the lab would have been much less enjoyable. I would like to thank my
partner in crime, Dan Denevan. It was always nice having Dan to make jokes with and to
have around to complain to about everything going wrong in the lab. I would also like to
thank Dr. Ana Ison for all of her support during this process. Ana was always around to
discuss ideas about projects. I would also like thank her for the help she provided in
acquiring the GC data. I would especially like to thank Dr. Celeste Regino. Celeste
taught me the intricacies of HPLC and that in order for it to do what you want you must
coddle it at all times.
I would also like to thank Pat Butler for all of her hard work during my elementary
education. As my SLD teacher, Mrs. Butler worked with me constantly for many years
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to help me cope with a disability I never thought I would be able to overcome. Now, as I
finish my dissertation to achieve my Ph.D., I appreciate even more all of the techniques
she taught me to help me achieve my goals.
I could not have accomplished this goal without the support of my family,
especially my parents. My parents have always supported me in all of the decisions I
have made and attending graduate school was no exception. Without their support, I
would never have had the courage to face new challenges and persevere in the face of
opposition.
I would also like to thank my wife, Erin. I never expected to meet my wife in
graduate school, nor did I expect her to be a chemistry graduate student. She has been a
constant support these past 5 years, and I would have given up this dream long ago were
it not for her constant vigilance in driving me toward my goal.
Most of all, I would like to thank God for all of His love and support through not
only my graduate career, but my entire life. Through Him all things are possible.
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TABLE OF CONTENTS

page
ACKNOWLEDGMENTS.................................................................................................iv
LIST OF TABLES.............................................................................................................ix
LIST OF FIGURES.............................................................................................................x
ABSTRACT.......................................................................................................................xx
CHAPTER
1 INTRODUCTION........................................................................................................1
General Oxidation.........................................................................................................1
Reactive Oxygen Species.............................................................................................3
Hydrogen Peroxide.......................................................................................................4
Activation of Hydrogen Peroxide.................................................................................6
UV Activation.......................................................................................................6
Strong Base Activation..........................................................................................7
Strong Acid Activation..........................................................................................8
Acyl Hydroperoxides.............................................................................................8
Iron(II) Activation.................................................................................................9
Transition-metal Organometallic Complexes......................................................10
Methyltrioxorhenium...........................................................................................11
Asymmetric Oxidation................................................................................................12
Sharpless Oxidation of Allylic Alcohols.............................................................12
Mn(III)-salen Epoxidation Catalysts...................................................................13
Chiral Ketone Epoxidation Catalysts..................................................................15
Peroxycarbonate.........................................................................................................16
Transition-metal Peroxycarbonate Complexes....................................................19
Transition-metal Activation of Peroxycarbonate in Solution..............................22
Scope of the Dissertation............................................................................................23
2 OXIDATION OF NUCLEOPHILIC ALKENES IN AQUEOUS MICELLAR
MEDIA.......................................................................................................................25
Introduction.................................................................................................................25
Results and Discussion...............................................................................................28
Styrene Oxidation in Micellar Media in the Absence of Mn(II).........................28
vi
Large Scale Styrene Oxidation............................................................................28
Styrene Oxidation in Micellar Media in the Presence of Mn(II).........................31
Reaction Kinetics.................................................................................................34
Dependence of Styrene Oxidation on Surfactant Identity...................................35
Dependence of Styrene Oxidation on the Manganese(II) Source.......................36
Bicarbonate Dependence.....................................................................................37
Experimental...............................................................................................................38
Materials and Instrumentation.............................................................................38
Standardization of Sodium Bicarbonate Solutions..............................................39
Styrene Oxidation Reactions...............................................................................40
Large Scale Styrene Oxidations..........................................................................40
Synthesis of Mn(DS) ..........................................................................................41
2
Styrene Oxidation in SDS with Mn(II) and Mn(DS) .........................................41
2
3 KINETIC INVESTIGATIONS OF THE MANGANESE(II) CATALYZED
DISPROPORTIONATION OF HYDROGEN PEROXIDE IN THE PRESENCE
OF BICARBONATE AND THE COMPARISON TO NUCLEOPHILIC
ALKENE EPOXIDATION........................................................................................42
Introduction.................................................................................................................42
Results and Discussion...............................................................................................44
Kinetics of Hydrogen Peroxide Decomposition..................................................44
Manganese(II) Dependence..........................................................................47
Bicarbonate Dependence..............................................................................48
Comparison of Hydrogen Peroxide Reaction Kinetics to Nucleophilic Alkene
Epoxidation Kinetics........................................................................................50
Manganese dependence on nucleophilic alkene epoxidation.......................50
Bicarbonate dependence on nucleophilic alkene epoxidation......................51
Hydrogen peroxide dependence on nucleophilic alkene epoxidation..........52
Catalyst Lifetime Studies....................................................................................53
Examining the loss of activity......................................................................54
Multiple additions of distilled hydrogen peroxide and solid sodium
bicarbonate................................................................................................55
Studies of the Manganese Source........................................................................56
Potassium permanganate..............................................................................56
[MnIV(Me TACN)(OMe) ]PF .....................................................................57
3 3 6
Mn(IV) catalyst stability..............................................................................57
Cis-trans Isomerization in the Manganese(II) Catalyzed Alkene Epoxidation...61
Cis/Trans isomerization reactions with cis-2-butene-1,4-diol.....................65
Cis/Trans isomerization of maleic and fumaric acids..................................65
Examination of Sychev’s Radical Trap Experiments..........................................68
Proposed Mechanism of N-dealkylation.............................................................81
Support for the Single Electron Transfer Pathway..............................................85
Solvent Isotope Effect.........................................................................................86
Proposed Mechanism...........................................................................................90
Numerical Simulation of the Proposed Mechanism............................................93
Conclusions...............................................................................................................109
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Experimental.............................................................................................................113
Materials and Instrumentation...........................................................................113
Standardization of sodium bicarbonate solutions.......................................114
Hydrogen peroxide decomposition studies................................................115
Synthesis of [MnIV(Me TACN)(OMe) ](PF )...........................................115
3 3 6
Oxidation of N,N-dimethyl-4-nitrosoaniline (DMNA) by Oxone.............116
Oxidation of N,N-Dimethyl-4-nitrosoaniline (DMNA) by H O /HCO -
2 2 3
/Mn2+.......................................................................................................116
Oxidation of N,N-diethyl-4-nitrosoaniline (DENA) by H O /HCO -/Mn2+117
2 2 3
4 ELECTROPHILIC ALKENE EPOXIDATION BY THE
PEROXYCARBONATE DIANION........................................................................118
Introduction...............................................................................................................118
Results and Discussion.............................................................................................119
Effect of Mn(II) on Electrophilic Alkene Epoxidation.....................................121
Effect of pH on the Oxidation of Electrophilic Alkenes...................................125
Effect of Buffer Choice on Electrophilic Alkene Epoxidation.........................130
Electrophilic Alkene Oxidation Kinetics...........................................................131
Discussion of the Second-Order Rate Constants...............................................133
Conclusions...............................................................................................................139
Materials and Instrumentation..................................................................................142
Experimental.............................................................................................................143
Electrophilic Alkene Epoxidation.....................................................................143
Dibenzoylethylene Kinetics...............................................................................143
5 GENERAL CONCLUSIONS...................................................................................144
APPENDIX: VARIATIONS IN NUCLEOPHILIC ALKENE EPOXIDATION AND
HYDROGEN PEROXIDE RATE CONSTANTS...................................................152
LIST OF REFERENCES.................................................................................................155
BIOGRAPHICAL SKETCH...........................................................................................163

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LIST OF TABLES
Table page

1-1 Some common reactive oxygen species.....................................................................3
2-1 Comparison of Styrene Oxidation in CTACl and SDS for the Mn(II) catalyzed
epoxidation. Reaction conditions: 0.05 M Styrene, 0.100 M CTACl or SDS,
0.25 M NH HCO , 1.00 M H O , and 10 µM Mn(II). Errors are reported to the
4 3 2 2
95% confidence........................................................................................................36
2-2 Comparison of observed rate constants for differing manganese sources for
micellar styrene oxidation. Reaction conditions: 0.05 M Styrene, 0.100 M SDS,
0.25 M NH HCO , 1.00 M H O , and 10 µM Mn(II) or Mn(DS) . Errors are
4 3 2 2 2
reported to the 95% confidence................................................................................37
3-1 Comparison of observed rate constants for the decomposition of hydrogen
peroxide, 0.100 M, in 0.20 M sodium bicarbonate with 3 and 4 µM
manganese(II) and permanganate. Errors reported are to the 95% confidence.......56
3-2 Comparison of observed rate constants for the decomposition of hydrogen
peroxide (0.100 M, final concentration) in 0.20 M sodium bicarbonate with 3
and 4 µM manganese(II) and [MnIV(Me TACN)(OMe) ](PF ). Errors reported
3 3 6
are to the 95% confidence........................................................................................61
3-3 Comparison of first-order rate constants for the epoxidation of sulfonated
styrene in H O and D O. Reaction conditions: 0.001 M SS, 1.0 M Sodium
2 2
Bicarbonate, 0.50 µM Mn(II)...................................................................................86
3-4 Comparison of solvent isotope effect for hydrogen peroxide decomposition.
Reaction Conditions: 0.40 M HCO -, 0.10 M H O .................................................90
3 2 2
4-1 The percent conversion of 1 in varying buffer at differing pH..............................131
4-2 pK values in water and CTACl for several different dyes.151...............................139
a

ix
LIST OF FIGURES
Figure page

1-1 The sulfate dianion.....................................................................................................1
1-2 The oxidation of organic molecules is defined as formation of bonds to carbon
with atoms that are more electronegative than carbon. Reduction is the loss of
bonds to more electronegative atoms and bond formation with hydrogen................3
1-3 Superoxide dismutase enzymatically oxidizes the superoxide anion and two
protons to hydrogen peroxide, another reactive oxygen species. Hydrogen
peroxide is the disproportionated by catalase to yield water and molecular
oxygen........................................................................................................................4
1-4 The AO-process for the industrial production of hydrogen peroxide........................5
1-5 Illustration of a nucleophilic attack on hydrogen peroxide. The use of a general
acid facilitates the proton transfer to yield the oxidized nucleophile and water........6
1-6 The reactivity of olefins with hydroxyl radicals.11.....................................................7
1-7 Polymerization of olefins by hydroxyl radical.11.......................................................7
1-8 Reactivity of electrophilic olefins with nucleophilic oxidants, such as
hydroperoxide, react to produce the epoxide plus the oxidants’ corresponding
leaving group, in this case hydroxide.........................................................................7
1-9 The reaction of an alkene with OH+ generates an intermediate carbocation. A
general base can then deprotonate the oxygen of the intermediate which results
in ring closure to form the epoxide............................................................................8
1-10 Alkene oxidation by m-CPBA....................................................................................9
1-11 Activation of iron(III) tetrakis(pentafluorophenyl) porphyrin by hydrogen
peroxide to produce a high oxidation state iron complex.20.....................................11
1-12 The two dominant forms in the MTO/H O system under acid conditions. The
2 2
diperoxorhenium adduct reacts slightly slower than the monoperoxorhenium
complex.23................................................................................................................12
x