Carbene Chemistry

Carbene Chemistry

2nd Edition - January 1, 1971

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  • Author: Wolfgang Kirmse
  • eBook ISBN: 9780323161459

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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

Product details

  • No. of pages: 634
  • Language: English
  • Copyright: © Academic Press 1971
  • Published: January 1, 1971
  • Imprint: Academic Press
  • eBook ISBN: 9780323161459

About the Author

Wolfgang Kirmse

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