An Ordering Concept on the Basis of Alternative Principles in Chemistry: Design of Chemicals and Chemical Reactions by Differentiation and Compensatio

ISBN-13: 9783642838088 / Angielski / Miękka / 2011 / 214 str.

Paul Heimbach; Tamas Bartik

Opis

Considering aspects of symmetry rules in chemistry, one is faced with con tradictory terms as for example, "90 % concertedness" sometimes being used in literature. To accept conservation of orbital symmetry to be as controlled as inversion by alternative principles seems far more promising. The intention of this book is aimed at introducing a qualitative understanding of phase rela tions in electromagnetic interactions. Avoiding one-sided dogmatism we tried to demonstrate the importance of alternative principles as guidelines to the evolution of alternative order in chemical systems. Passing through the jungle of information it became extremly important to control again and again our insights into the ordering phenomena by experi ments under conditions as coherent as possible. We became more aware of the fact that chemistry - the science of "becoming" in complex systems - can not be understood by mechanistic details, i. e. THROUGHPUT-studies alone, because the mechanism is only true for the special system under inves tigation and does not offer a tool for the evolution of opposite order. We had to accept chemistry as a mediator between molecular physics and general epistemology. This quite unusual combination was directed by excel lent teachers and the realizations were made possible by enthusiastic, open minded coworkers (see references). The next target we will strive for on this journey will be to quantify the alternative principles, that means obtaining the order parameters of H. Haken (e. g. in asymmetric synthesis)."

Spis treści

1 Introduction.- 2 Characterization of Substituents by Patterns and Recognition of ALTERNATIVE PRINCIPLES.- 2.1 Correlation with the Parameter Sets ? and ? by Tolman.- 2.2 Systematic Variations at Tetrahedral Centers: A New Parameter Set ?.- 2.3 The Importance of the Representative Substituents -OMe/-SMe and -CMe3/-SiMe3.- 2.4 The Importance of P- and ?-parameter Sets for Pattern Comparison.- 2.5 The Importance of Compensation Phenomena.- 2.6 Further Characterization of Substituents by Pattern Comparison.- 2.7 Conformational Changes in Phenyl Systems.- 3 Examples of Absolute, Alternative Orders in Chemical Systems by Pairs and Alternating Classes of ALTERNATIVE PRINCIPLES.- 3.1 Examples for the Absolute, Alternative Effects by ACC/DO Heteroatoms.- 3.2 Separation of Main Group and Transition Metal Elements in Four Sectors (PSE-sectors).- 3.3 Errors of Logical Typing in DO/ACC Alternatives.- 3.4 The Alternative Principles EVEN/ODD.- 3.5 Aspects of Coupling Chemical Subsystems: The Alternative Principles OPEN/CYCLIC.- 3.6 The Metala-Logy Principle.- 3.7 The Principle of Alternative Positions.- 3.8 The Alternative Principles IONIC/COVALENT.- 4 Representation of Differentiation and Compensation of ALTERNATIVE PRINCIPLES.- 4.1 On the Definition of Paritetic and Complementary ALTERNATIVE PRINCIPLES and their Effects.- 4.2 Differentiation and Compensation of Two Pairs of AL lERNATIVE PRINCIPLES.- 4.3 Alternative Patterns by Classes of ALTERNATIVE PRINCIPLES.- 4.4 Symmetric/ Antisymmetric Coupling of Two Pairs of ALTERNATIVE PRINCIPLES.- 4.5 Representation in Hierarchically Ordered, Multi-dual Decision-trees.- 5 Representative Examples of Multi-dual Decision — Trees: A Generalization of Phase Relation Rules.- 5.1 The Control of Elimination Reactions by ALTERNATIVE PRINCIPLES.- 5.2 The Alternative Control of Knoevenagel Versus Michael Reaction of Mesityloxide.- 5.3 Control of Asymmetric Synthesis in a Metal-induced Ketone Synthesis.- 5.4 Influence on Structures and Processes in Transition Metal Complexes.- 5.5 A Comparison of the Catalytic Oligomerizations of Propanal.- 6 The Discontinuous Method of INVERSE TITRATION.- 6.1 Evidence in Support of Concentration Effects: A Summary.- 6.2 Examples for the Application of INVERSE TITRATION.- 6.2.1 Application of INVERSE TITRATION in Metal Catalysis.- 6.2.2 Application of the INVERSE TITRATION in Organic Syntheses.- 6.2.3 Application of INVERSE TITRATION in SYSTEM ENLARGEMENT.- 6.2.4 Application of INVERSE TITRATION for the Proof of the Influence of Catalyst Poisons.- 6.2.5 Aspects in Application of INVERSE TITRATION for the Ni-ligand Modified Catalytic Propene Dimerization.- 6.3 Outlook and Unsettled Problems.- 7 Molecular Architecture: Some Definitions.- 7.1 Structure of the Whole System.- 7.2 Intermolecular SYSTEM ENLARGEMENT.- 7.3 Intramolecular SYSTEM ENLARGEMENT and VARIATION: Substitution of Hydrogen by Substituents and Carbon by Heteroatoms.- 7.4 Coupling of Subsystems.- 7.5 Symmetry Aspects in the Coupling of Chemical Subsystems.- 8 Models and Methods for the Understanding of Self-organization and Synergetics in Chemical Systems.- 8.1 The Ordering CONCEPT OF ALTERNATIVE PRINCIPLES in a Comprehensive Form.- 8.2 Some Statements to the Application of the CONCEPT OF ALTERNATIVE PRINCIPLES.- 8.3 Application of the CONCEPT OF ALTERNATIVE PRINCIPLES as Compensation Strategy.- 9 Information from Alternatives in Biochemistry.- 9.1 Alternative Information on Nucleic Acids and ?-Amino-Carboxylic Acids.- 9.2 Alternative Information at Bio-membranes.- 9.3 Chirality, an Error in Logical Typing.- 9.4 Restriction of the Number of Realizations in Evolved Systems.- 10 Acknowledgements and Petition.- 11 Appendix.- 12 References.- 13 Epilogue.