Organic and bio-organic mechanisms:
Gespeichert in:
| Hauptverfasser: | , |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Harlow
Addison Wesley Longman
1997
|
| Ausgabe: | 1. publ. |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | X, 298 S. zahlr. Ill., graph. Darst. |
| ISBN: | 0582074843 |
Internformat
MARC
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| 100 | 1 | |a Page, Michael I. |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Organic and bio-organic mechanisms |c Michael Page and Andrew Williams |
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Datensatz im Suchindex
| _version_ | 1804127135176065024 |
|---|---|
| adam_text | Titel: Organic and bio-organic mechanisms
Autor: Page, Michael I.
Jahr: 1997
Contents
Preface ix
1 THE TRANSITION STATE /
1.1 Mechanism as a progression of states 1
1.2 Structure and its interpretation /
1.3 Interconversion of states—reaction and encounter
complexes 4
1.4 Methods of representing reaction mechanisms 4
1.5 General considerations concerning reaction mechanisms 6
1.6 Energy transfer, redistribution and relaxation 12
1.7 Stereoelectronic effects 16
1.8 Principle of non-perfect synchronization 18
1.9 Principle of least nuclear motion 19
1.10 Is the transition state a molecule? 19
2 Kinetics and mechanism 23
2.1 Introduction 23
2.2 Kinetic method 24
2.3 Rate law and mechanism 25
2.4 Steady state and non-steady state 25
2.5 Rate-limiting step 26
2.6 Curtin-Hammett principle 28
2.7 Which transition state is being observed kinetically? 29
2.8 Demonstration of intermediates by kinetics 30
2.9 Change in mechanism 33
2.10 Rules for change in mechanism or rate-limiting step 36
2.11 Trapping of intermediates 37
2.12 Composition of the transition state of the rate-limiting step 38
2.13 Kinetic ambiguities 40
2.14 Microscopic reversibility 42
2.15 Kinetic and thermodynamic control 43
2.16 Isotope labelling techniques and detection of intermediates 45
vi Contents
3 The effect of changes in reactant structure 52
3.1 Introduction 52
3.2 Comparison of known with unknown—the Leffler
approach 52
3.3 Polar and steric substituent effects 55
3.4 Hammett s equation 55
3.5 Bransted s equation 62
3.6 Transition-state acidity and transition-state complexation 74
3.7 Topology of transition states 75
4 Kinetic and equilibrium isotope effects 80
4.1 Origin of isotope effects 80
4.2 Measurement of kinetic isotope effects 84
4.3 Primary isotope effects 86
4.4 Solvent isotope effects 88
4.5 Heavy-atom isotope effects 92
4.6 Secondary isotope effects and transition-state structure 94
5 Transition states from external effects 97
5.1 Introduction 97
5.2 Solvent effects 97
5.3 Reactions in strongly acidic and strongly basic media 101
5.4 Solvent ionizing power 105
5.5 Variation of pressure and temperature 107
6 Transition state structures—anomalies 116
6.1 Introduction 116
6.2 Reactivity-selectivity relationship 116
6.3 Microscopic medium effects 121
6.4 Curvature in free-energy relationships 123
6.5 Bransted anomalies 128
6.6 Do experimental parameters directly measure transition-state
structures? 130
7 Bio-organic group transfer reactions 134
7.1 Relative timing of bond formation and bond fission 134
7.2 Acyl group transfer 145
8 Catalysis 161
8.1 Reactivity 161
8.2 Coenzymes 166
8.3 Proton transfer 174
8.4 Metal ions 179
8.5 Intramolecular reactions 184
Contents vii
9 COMPLEXATION CATALYSIS 196
9.1 General considerations 196
9.2 Covalent catalysis 198
9.3 Inclusion complexation 199
9.4 Catalysis by organized aggregates and phases 205
9.5 Future directions 212
10 Some enzymes 214
10.1 Introduction 214
10.2 Enzymes catalysing acyl group transfer 215
10.3 Catalysis of proton transfer reactions 224
10.4 Carbon-carbon bond formation and fission 232
10.5 Transfer of the hydride ion 235
10.6 Alkyl group transfer 240
Appendices
A.I IUPAC system for symbolic representation of reaction
mechanisms 247
A.2 Supplementary tables 248
A. 3 Estimation of ionization constants 258
A.4 Estimation of partition coefficients 261
A.5 Fitting data to theoretical equations 264
References 267
Index 291
Viewing the stereo-diagrams
This book includes stereoscopic images which consist of two non-intersecting
half-pictures. With a little practice these can yield stereoscopic views with
the naked eye. Stereoscopic viewing devices such as that designed by
Vogtle and Schuss provide an easier method of visualization: these are
commercially available.
|
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| discipline | Chemie / Pharmazie |
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| id | DE-604.BV012491375 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T18:28:32Z |
| institution | BVB |
| isbn | 0582074843 |
| language | English |
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| physical | X, 298 S. zahlr. Ill., graph. Darst. |
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| spelling | Page, Michael I. Verfasser aut Organic and bio-organic mechanisms Michael Page and Andrew Williams 1. publ. Harlow Addison Wesley Longman 1997 X, 298 S. zahlr. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Chimie organique physique ram Réactions chimiques - Mécanismes ram Chemical reactions Chemistry, Organic Reaktionsmechanismus (DE-588)4177123-0 gnd rswk-swf Biochemie (DE-588)4006777-4 gnd rswk-swf Organische Chemie (DE-588)4043793-0 gnd rswk-swf Reaktionsmechanismus (DE-588)4177123-0 s Organische Chemie (DE-588)4043793-0 s DE-604 Biochemie (DE-588)4006777-4 s Williams, Andrew Verfasser aut HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008479407&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Page, Michael I. Williams, Andrew Organic and bio-organic mechanisms Chimie organique physique ram Réactions chimiques - Mécanismes ram Chemical reactions Chemistry, Organic Reaktionsmechanismus (DE-588)4177123-0 gnd Biochemie (DE-588)4006777-4 gnd Organische Chemie (DE-588)4043793-0 gnd |
| subject_GND | (DE-588)4177123-0 (DE-588)4006777-4 (DE-588)4043793-0 |
| title | Organic and bio-organic mechanisms |
| title_auth | Organic and bio-organic mechanisms |
| title_exact_search | Organic and bio-organic mechanisms |
| title_full | Organic and bio-organic mechanisms Michael Page and Andrew Williams |
| title_fullStr | Organic and bio-organic mechanisms Michael Page and Andrew Williams |
| title_full_unstemmed | Organic and bio-organic mechanisms Michael Page and Andrew Williams |
| title_short | Organic and bio-organic mechanisms |
| title_sort | organic and bio organic mechanisms |
| topic | Chimie organique physique ram Réactions chimiques - Mécanismes ram Chemical reactions Chemistry, Organic Reaktionsmechanismus (DE-588)4177123-0 gnd Biochemie (DE-588)4006777-4 gnd Organische Chemie (DE-588)4043793-0 gnd |
| topic_facet | Chimie organique physique Réactions chimiques - Mécanismes Chemical reactions Chemistry, Organic Reaktionsmechanismus Biochemie Organische Chemie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008479407&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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