Carbene Chemistry - 2nd Edition - ISBN: 9780124099562, 9780323161459

Carbene Chemistry

2nd Edition

Authors: Wolfgang Kirmse
eBook ISBN: 9780323161459
Imprint: Academic Press
Published Date: 1st January 1971
Page Count: 634
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Carbene Chemistry, Second Edition discusses the developments in various areas of carbene chemistry, including the correlation of spectroscopic studies of isolated carbenes with quantum chemical calculations; new carbene precursors; differentiation of carbenes and carbenoids; and mechanisms of single and triplet carbine reactions. This book is composed of two main parts encompassing 13 chapters. The first part covers the many reactions known to transfer a formally divalent carbon fragment from one molecule to another, with special emphasis on the mechanism and a critical evaluation of the evidence for carbene intermediates. The second part examines the multitude of product-forming reactions of carbenes and carbenoids with various substrates. This part also describes the structure-reactivity relationships for both carbenes and their substrates, followed by a discussion of the applications of carbene compounds in synthetic organic chemistry. This work will be of great value to organic chemists and researchers.

Table of Contents

Preface to Second Edition

Preface to First Edition

Part I Methylene Transfer Reactions

Chapter 1 Introduction

I. Examples of Methylene Transfer

II. Mechanisms of Methylene Transfer

III. Carbenes and Carbenoids

Review Literature On Carbenes

Chapter 2 Photochemical and Thermal Methylene Transfer Reactions

I. Photolysis of Ketene

II. Photolysis of Alkyl- and Arylketenes

III. Photolysis of Carbon Suboxide

IV. Photolysis of Diazo Compounds

V. Pyrolysis of Diazo Compounds

VI. Bamford-Stevens Reaction

VII. Decomposition of Diazirines

VIII. Decomposition of Cyclopropanes

IX. Photolysis of Oxiranes

X. Pyrolysis of 7-Norbornadienone Ketals

XI. Rearrangement of Carbonyl Compounds

XII. Decomposition of Polyhalomethanes

XIII. Decomposition of Alkanes

XIV. Reactions of Atomic Carbon

XV. Decomposition of Olefins

XVI. Desulfurization and Deoxygenation Reactions

XVII. Decomposition of Ylides


Chapter 3 Organometallic Methylene Transfer Agents

I. Catalytic Decomposition of Diazoalkanes

II. Simmons-Smith Reaction

III. Organolithium Reagents

IV. Organomercury Reagents

V. Organosilicon and Organotin Reagents

VI. Carbene Complexes of the Transition Metals


Chapter 4 Base-Induced α-Elimination

I. Basic Hydrolysis of Haloforms

II. Trihalomethides in Aprotic Media

III. α-Elimination at Methylene Halides

IV. Dehydrohalogenation of Benzylic Halides

V. Solvolysis of Propargyl and Allenyl Halides

VI. α-Elimination at Alkyl Halides

VII. Deprotonation of Carbonium Ions


Part II Structure and Reactivity of Carbenes and Carbenoids

Chapter 5 the Structural Theory of Carbenes

I. An Approach To the Electronic Structure Of Carbenes

II. the Electronic Structure of CH2

III. Use of Extended Hückel Theory in the Elucidation of Carbene Structure

IV. Halocarbenes

V. Charge Distribution

VI. Conclusions


Chapter 6 the Spectra of Carbenes

I. Electronic and Vibration-Rotation Spectroscopy

II. Electron Spin Resonance (ESR) Spectroscopy


Chapter 7 Reactions with Carbon-Hydrogen Bonds

I. Insertion and Abstraction Mechanisms

II. Stereochemistry

III. Selectivity

IV. Intramolecular Insertion


Chapter Addition to Alkenes

I. Stereospecificity

II. Stereoselectivity

III. Reactivity

IV. Synthesis of Cyclopropanes

V. Addition Accompanied By Rearrangement

VI. Intramolecular Addition


Chapter 9 Addition to Alkynes

I. Formation of Cyclopropenes

II. Formation of Bicyclobutanes

III. Reactions with Enynes

IV. Addition Accompanied By Rearrangement

V. "1,3-Dipolar Additions" of Carbonylcarbenes

VI. Thermal Reactions of Dialkyl Acetylene Dicarboxylates


Chapter 10 Addition to Arenes

I. Aromatic Carbocyclic Compounds

II. Aromatic Heterocyclic Compounds

III. Intramolecular Reactions


Chapter 11 Reactions Involving Hetero Atoms

I. Sllanes and Germanes

II. Nitrogen Compounds

III. Organophosphorus Compounds

IV. Oxygen Compounds

V. Organosulfur Compounds

VI. Organic Halides

VII. Organometallic Compounds


Chapter 12 Rearrangements

I. 1,2 Shifts in Alkylcarbenes

II. Cyclopropylidene-Allene Rearrangement

III. Rearrangement and Fragmentation of Cyclopropylcarbenes

IV. Cyclobutylidene-Methylenecyclopropane Rearrangement

V. Wolff Rearrangement of Diazo Ketones

VI. Rearrangement of Arylcarbenes


Chapter 13 Silicon, Germanium, AND Tin Structural Analogs of Carbenes

I. Introduction

II. Silicon Dichloride, :SiCl2

III. Silicon Dibromide and Diiodide, SiBr2 and SiI2

IV. Chlorosilyene and Bromosilyene, HSiCl and HSiBr

V. Silicon Difluoride, SiF2

VI. Silylene, SiH2

VII. Silicon Atoms, Si

VIII. Alkyl- and Arylsilylenes, RSiH and RR'Si

IX. Silicon Monoxide and Silicon Monosulfide, SiO and SiS

X. Germanium Atoms, Ge

XI. Germylene, GeH2

XII. Dialkyl and Diaryl Germylenes, R2Ge

XIII. Germanium Dihalides, GeX2

XIV. Germanium Monoxide and Monosulfide, GeO and GeS

XV. Divalent Tin Compounds

XVI. Conclusion


Author Index

Subject Index


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© Academic Press 1971
Academic Press
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About the Author

Wolfgang Kirmse

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