Kozma CRC Handbook of Optical Resolutions via Diastereomeric Salt Formation

Erscheinungsjahr 2010
ISBN: 978-1-4200-4260-3
Verlag: Taylor & Francis
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 704 Seiten

Optically active compounds are gaining ever-increasing importance in organic chemistry, both in the academic and the industrial arenas. The rational synthesis of the growing number of chiral chemicals, drugs, and natural products demands efficient methods for producing these compounds in an enantiomerically, highly pure form. Despite the available alternative techniques, optical resolution via Diastereomeric salt formation remains the most widely used method of preparing pure enantiomers.

The CRC Handbook of Optical Resolutions Via Diastereomeric Salt Formation is the first book to exclusively address this important organic chemical process. It provides fast, one-stop access to a wealth of information, including all of the available data on 100 resolving agents, a list of 500 optically active compounds available in bulk along with their suppliers, data on more than 3,500 resolutions, and 4,200 citations.

This handbook helps answer virtually any question that may arise during the development of a new resolution process.

Which resolving agent and solvent should I use under these conditions?

How can I separate the diastereoisomers?

How can I optimize a resolution process?

How do I determine enantiomeric purity?

Which supplier has the resolving agent I need?

For a racemate already resolved, what were the resolving agent, solvent, and relevant citation?

This is the first book to deal exclusively with all aspects of this important organic chemical process, both theoretical and practical. With an abundance of analyzed examples, this single, authoritative reference provides all of the information you need to perform, develop, and optimize optical resolutions via Diastereomeric salt formation

Zielgruppe

Chemists, chemical engineers working in the fields of organic chemistry, pharmaceutical industry, and fine chemicals production

Autoren/Hrsg.

Kozma, David

Fachgebiete

• Naturwissenschaften Chemie Organische Chemie

Inhaltsverzeichnis

INTRODUCTION
BASIC CONCEPTS AND NOMENCLATURE OF STEREOCHEMISTRY
Chirality, Enantiomers and Diastereomers
Stereochemical Nomenclature
Principles of Separation of Diastereomers and Enantiomers
RESOLUTION BY FORMATION AND FRACTIONAL CRYSTALLISATION OF DIASTEREOMERIC SALTS
The Concept of Resolvability
Stoichiometry of Resolution
Resolution with One Equivalent of Resolving Agent
Resolution with Half Equivalent of Resolving Agent in Combination with an Achiral Additive
Use of Half Molar Equivalent of Resolving Agent without an Achiral Additive
Salt-Salt Resolution
Resolution with the Enantiomer of the Resolving Agent
Reciprocal Resolution
Mutual Resolution
Resolution with Difunctional Resolving Agents
Resolution of Amphoteric Racemates
Resolution by Salt Formation of Compounds Lacking Acidic or Basic Groups
Asymmetric Transformations during Resolution by Salt Formation
RESOLVING AGENTS
Basic Resolving Agents
Acidic Resolving Agents (Including Amino Acids)
RESEARCH ON RESOLVING AGENTS
Attempts to Devise A Generally Applicable Resolving Agent
Correlation of the Efficiency of Resolution with the Structure of Racemate and Resolving Agent.
Resolutions with a Derivative of the Racemate
Resolutions with a Mixture of Structurally Similar Resolving Agents
SELECTION OF THE RESOLVING AGENT
SELECTION OF THE RESOLVING AGENT BY EXPERIMENTATION
Selection of the Resolving Agent by Small-Scale Preliminary Preparative Experiments
Selection of the Resolving Agent by Combined Application of Several Resolving Agents
Selection of the Resolving Agent by Distillation Tests
Selection of the Resolving Agent Based on the Principle of Maximum Similarity
Selection of the Resolving Agent by Statistical Evaluation
SELECTION OF A RESOLVING AGENT BASED ON THE DETERMINATION OF PHYSICO-CHEMICAL PARAMETERS
Solubility
Selection of a Resolving Agent Based on Melting Point Phase Diagrams of Diastereomeric Salt Pairs
Calculation of Resolvability by DSC of a Mixture of Diastereomeric Salts Formed from the Racemate
Determination of the Optical Rotation of Diastereomeric salts
SELECTION OF THE RESOLVING AGENT BASED ON THEORETICAL CONSIDERATIONS
RESOLUTION IN PRACTICE, SELECTION OF THE OPTIMAL PARAMETERS
Reacting the Components
Initiation of Crystallisation
Role of Temperature in Resolution
Further Purification of Diastereomeric Salts with the Aid of a Chiral
Additive
Recovery of the Components from the Diastereomeric Salts
Upgrading of Optical Purity without a Chiral Additive (Enantiomeric Enrichment)
ALTERNATIVE METHODS OF RESOLUTION BY DIASTEREOMERIC SALT FORMATION
Classification of Alternative Resolution Processes by Type of Phase Transition
Resolution by Distillation
Resolution by Extraction
Resolution by Supercritical Extraction
Resolution by Sublimation
Mechanical Separation of Diastereomeric Salt Mixtures
DETAILED DESCRIPTIONS OF SELECTED RESOLUTIONS

APPENDIX 1: Resolutions Ordered According to the Resolving Agent
APPENDIX 2: Commercially Produced Resolving Agents and Optically Active Industrial Products which may be Eligible as Resolving Agents
APPENDIX 3. Chiral Selective Chromatographic Analysis