THE ROLE OF STRUCTURAL EFFECTS ON THE SIDE
CHAIN FRAGMENTATION PATHWAYS OF RING
METHOXYLATED ARYLALKANOIC ACID RADICAL
CATIONS
Alberto Capone
Dottorato in Scienze Chimiche XVIII ciclo
Il Supervisore Il Coordinatore di Dottorato
2
INDEX
GENERAL INTRODUCTION 4
References 11
CHAPTER 1
Materials and Methods 14
1.1 Materials 16
1.2 Generation of the Radical Cations 23
1.3 Product Studies 25
1.4 Time-Resolved Studies 26
1.5 DFT Calculations 27
CHAPTER 2
2.1 Spectroscopic Detection, Reactivity and Acid-Base Behavior of Ring Dimethoxylated Phenylethanoic Acid Radical Cations and Radical Zwitterions in Aqueous Solution.
2.1.1 Introduction 32
2.1.2 Results and Discussion 34
2.1.3 References 42
2.2 One-Electron Oxidation of 2-Aryl-2-Methyl Propanoic and
1-Arylcyclopropanecarboxylic Acids in Aqueous Solution. The
Involvement of Aromatic Radical Cations and the Effect of an αααα
3
2.2.1 Introduction 44
2.2.2 Results 45
2.2.3 Discussion 64
2.2.4 References 74
2.3 One-Electron Oxidation of Ring Methoxylated
1-Arylcycloalkanecarboxylic Acids. The Involvement of Aromatic Radical Cations and the Effect of Ring Size on the Decarboxylation Rate Constant.
2.3.1 Introduction 78
2.3.2 Results 79
2.3.3 Discussion 85
2.3.3 References 89
CHAPTER 3
Reactivity and Acid-Base Behavior of Ring-Methoxylated Arylalkanoic Acid Radical Cations and Radical Zwitterions in Aqueous Solution. The
Influence of Structural Effects and pH on the Benzylic C−−−−H Deprotonation
Pathway.
3.1 Introduction 92
3.2 Results and Discussion 93
