α-Aminoacid-N-Carboxy-Anhydrides and Related Heterocycles: Syntheses, Properties, Peptide Synthesis, Polymerization

ISBN-13: 9783642715884 / Angielski / Miękka / 2011 / 214 str.

Hans R. Kricheldorf

Opis

In 1906, Hermann Leuchs, a student of Emil Fischer, discovered the class of N-Carboxy-aminoacid-anhydrides, also known as Leuch's anhydrides, or abbreviated NCAs. These compounds are, even 80 years after their discovery, valuable intermediates in organic synthesis due to their reactivity: NCAs polymerize with the elimination of carbondioxide to yield polypeptides, model compounds for proteins. They can be used as starting material for a variety of pharmaceutically interesting products and for synthetic polymers (fibres and films). Ralph Hirschmann demonstrated the step by step synthesis of ribonuclease utilizing NCAs as monomers. The author of this monograph, Hans R. Kricheldorf, University Hamburg, is, on account of his own research in Freiburg and Hamburg, predestined to give the reader an insight into the organic chemistry of NCAs and related heterocycles as well as macromolecular chemistry, that is the synthesis of polypeptides and the structure-reactivity relationship. I predict a good accept ance of this book about the class of cyclic aminoacid derivatives by scientists in various areas. Aachen, September 1986 Helmut Zahn Acknowledgment The author would like to express his gratitude to the american chemical society, the royal society of chemistry, Marcel Dekker Inc., John Wiley & Sons, Hiithig & Wepf Verlag and Kobunshi Gakkai for the permission to reproduce figures from their journals."

Spis treści

1. Synthesis and Characterization of NCAs.- 1.1 Syntheses of ?-Amino Acid NCAs.- 1.2 Syntheses of ß- and ?-Amino Acid NCAs.- 1.3 Thio Analogs of ?- and ß-Amino Acid NCAs.- 1.4 Purification and Titration of NCAs.- 1.5 IR Spectroscopy.- 1.6 NMR Spectroscopy.- 1.7 Tables of NCAs.- References.- 2. Oligomerization and Polymerization of NCAs: Chemical Aspects..- 2.1 Background.- 2.2 Stoichiometric Reactions of NCAs.- 2.2.1 Reactions with Protic Nucleophiles.- 2.2.2 Various Reactions.- 2.3 Stepwise Peptide Syntheses.- 2.3.1 With N-Unsubstituted NCAs.- 2.3.2 With TV-Substituted NCAs.- 2.4 Polymerization with Protic Nucleophiles.- 2.4.1 Primary Amines.- 2.4.2 Secondary Amines.- 2.4.3 The Carbamate Mechanism.- 2.5 Tertiary Amines.- 2.5.1 Trialkylamines.- 2.5.2 Pyridines.- 2.6 Metal Salts and Organometallic Compounds.- 2.6.1 Various Anions.- 2.6.2 Organometallic Initiators.- 2.7 Thermal Polymerizations.- 2.8 ?-Amino Acid NCA and Thio NCAs.- 2.8.1 ?- and ?-Amino Acid NCAs.- 2.8.2 Thio Analogs of NCAs.- References.- 3. Polymerization of NCAs: Physical Aspects.- 3.1 Determination of Molecular Weights.- 3.1.1 Endgroup Analyses.- 3.1.2 Physical Methods.- 3.2 Molecular Weight Distributions and Polydispersity.- 3.3 Chain-Effect Polymerization.- 3.3.1 The Chain Effect of Polysarcosine.- 3.3.2 The Helical Chain Growth.- 3.3.3 Template Polymerizations.- 3.4 Secondary Structure of Solid Polypeptides.- 3.4.1 Definitions and Methods.- 3.4.2 Secondary Structure and Crystal Growth.- References.

O autorze

Hans Rytger Kricheldorf studierte Chemie an der Universität Freiburg. Nach seiner Promotion 1969 habilitierte er sich 1975 auf dem Gebiet der makromolekularen Chemie und wurde 1980 außerplanmäßiger Professor in Freiburg. Im Jahre 1982 übernahm er einen Lehrstuhl für Polymerchemie an der Universität Hamburg. Sein Spezialgebiet ist die Polykondensation.