Part I Reductive alkylation of acenaphthylene

Contents

Chapter 1

1.1 General introduction 1

1.2 Aromaticity 4

1.3 Reduction and reductive alkylation of PAHs 8

1.4 Acenaphthylene 10

1.5 Purpose of this investigation 12

1.6 References 13

Part I Reductive alkylation of acenaphthylene

Chapter 2

2.1 Introduction 21

2.2 Results 21

2.2.1 Reactions with electrophiles 21 2.2.2 ¹H and ¹³C NMR spectroscopy 22 2.2.3 Ab initio calculations 26

2.3 Discussion 27

2.4 Conclusions 29

2.5 Experimental section 30

2.6 References 32

Chapter 3

3.1 Introduction 35

3.2 Results 35

3.3 ¹H and ¹³C NMR spectroscopy 37

3.4 Discussion 38

3.5 Conclusions 41

3.6 Experimental section 41

3.7 References 46

Chapter 4

single electron transfer vs. SN2

4.1 Introduction 47

4.2 Results 47

4.3 ¹H and ¹³C NMR spectroscopy 49

4.4 Discussion 50

4.5 Conclusions 54

4.6 Experimental section 55

4.7 References 60

Chapter 5

5.1 Introduction 61

5.2 Results and discussion 62

5.3 Conclusions 67

5.4 Experimental section 67

5.5 References 72

Chapter 6

6.1 Introduction 73

6.2 Results 73

6.3 Discussion 75

6.4 Conclusions 79

6.5 Experimental section 80

6.6 References 84

Part II Reduction of substituted acenaphthylenes

Chapter 7

7.1 Introduction 87

7.2 Results and discussion 88 7.2.1 Synthesis of 1- and 5-substituted acenaphthylenes 88 7.2.2 Reduction of 1- and 5-substituted acenaphthylenes 90

7.2.3 Cyclic voltammetry 92

7.3 Conclusions 95

7.4 Experimental section 96

7.5 References 104

Chapter 8

8.1 Introduction 105

8.2 Results 105

8.2.1 Reductive methylation 105 8.2.2 ¹H and ¹³C NMR spectroscopy 107

8.2.3 Quantum chemical calculations 110

8.3 Discussion 114

8.4 Conclusions 119

8.5 Experimental section 120

8.6 References 126

Chapter 9

9.1 Introduction 127

9.2 Results and discussion 127

9.2.1 1-Methylacenaphthylene 127 9.2.2 5-Methylacenaphthylene 130

9.3 Conclusions 133

9.4 Experimental section 134

9.5 References 136

Chapter 10

Summary

Samenvatting

Curriculum Vitae

Nawoord