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Dehydrobenzene and Cycloalkynes - 1st Edition - ISBN: 9780123957535, 9780323162807

Dehydrobenzene and Cycloalkynes

1st Edition

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Author: Reinhard W. Hoffmann
eBook ISBN: 9780323162807
Imprint: Academic Press
Published Date: 1st January 1967
Page Count: 398
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Dehydrobenzene and Cycloalkynes deals with the problems associated with the production and reactions of dehydrobenzene and of the related fields of dehydroheterocycles and cycloalkynes.

This book also describes the various synthetic applications of dehydrobenzene and provides a list of reactions in which dehydrobenzene occurs as an intermediary. The text explains the generation of dehydrobenzene by cleavage of cyclic systems, by photolytic methods, and by free radical reactions. Nucleophilic and electrophilic monodentate attacks on dehydrobenzene, as well as, bidentate additions to dehydrobenzene yielding cycloadducts. The book also notes that dehydrobenzene is not only a transition state but can be an intermediate of characteristic selectivity and lifetime. The reactions of dehydrobenzene in the gaseous phase affirm that the existence of dehydrobenzene is not restricted to the presence of a solvation shell. The researcher can then study the molecular structure of dehydrobenzene when its existence has been fully established. The text also extends the principle that the dehydroaromatic intermediates can be obtained by abstracting two adjacent hydrogen atoms from an aromatic substrate different from the 1- and 2- positions to arrive at a 1,3- and 1,4-dehydrobenzene.

Researchers and scientists whose works are associated with organic chemistry, analytical chemistry, molecular physics or physical chemistry will find this book valuable.

Table of Contents


Nomenclature and Formulae

General References



Chapter 1 Formation of Dehydrobenzene

1.1. Formation of Dehydrobenzene from Orthο-Anionized Benzene Derivatives

1.1.1. Halides as Leaving Groups

1.1.2. Other Anionic Leaving Groups in Ortho-Anionized Benzene Derivatives

1.1.3. Neutral Molecules as Leaving Groups from Ortho-Anionized Benzene Derivatives

1.2. Generation of Dehydrobenzene by Cleavage of Cyclic Systems

1.2.1. Cleavage of Heterocycles with Loss of Molecular Nitrogen

1.2.2. Further Attempts of Obtain Dehydrobenzene by Ring Cleavage

1.3. Generation of Dehydrobenzene by Photolytic Methods and by Free Radical Reactions


Chapter 2 Polar Additions to Dehydrobenzene

2.1.1. Nucleophilic Additions of Anions and their Conjugate Acids to Dehydrobenzene

2.1.2. Order of Nucleophilicity Towards Dehydrobenzene

2.2. Addition of Nucleophiles to Unsymmetrically Substituted Dehydroaromatic Intermediates

2.2.1. The Isomer Ratio as a Function of the Substituent Present

2.2.2. The Isomer Ratio as a Function of the Attacking Nucleophile

2.3. Ring Closure Reactions Via Polar Addition to Dehydroaromatic Intermediates

2.4. Addition of Nucleophiles to Dehydrobenzene to Form Betaines and Ylides

2.4.1. Addition of Sulfides to Dehydrobenzene

2.4.2. Addition of Neutral Phosphorus Compounds to Dehydrobenzene

2.4.3. Addition of Tertiary Amines to Dehydrobenzene

2.4.4. The Reaction of Dehydrobenzene with Ethers and N-Oxides

2.4.5. Electrophilic Attack of Dehydrobenzene at Unsaturated Carbon Atoms

2.5. Addition of Electrophiles to Dehydrobenzene


Chapter 3 Reactions of Dehydrobenzene with Nonpolar Partners

3.1. Reduction of Dehydrobenzene

3.2. Reaction of Dehydrobenzene with Carbon Hydrogen Bonds

3.2.1. "Insertion" Reactions

3.2.2. Ene Reactions

3.3. Cycloadditions Involving Dehydrobenzene

3.3.1. Cycloadditions Leading to Three-Membered Rings

3.3.2. Cycloadditions Leading to Four-Membered Rings

3.3.3. Cycloadditions Leading to Five-Membered Rings

3.3.4. Diels-Alder Additions

3.3.5. Further Cycloadditions


Chapter 4 Radical Reactions of Dehydrobenzene


Chapter 5 Structure and Reactivity of Dehydrobenzene

5.1. The Selectivity of Dehydrobenzene

5.2. The Structural Features of Dehydrobenzene

5.3. Existence of Dehydrobenzene in the Gas Phase

5.4. The Structure of Dehydrobenzene


Chapter 6 Dehydroheterocyclic Intermediates

6.1. Generation of Dehydroheterocyclic Intermediates from Ortho-Anionized Halogeno Heterocycles

6.1.1. Reaction of Halogeno Heterocycles with Base

6.1.2. Other Routes to Ortho-Anionized Halogeno Heterocycles

6.1.3. Stability of the Ortho-Anionized Halogeno Heterocycles

6.2. Other Methods of Generating Dehydroheterocyclic Intermediates

6.3. Polar Additions to Dehydroheterocyclic Intermediates

6.3.1. Substituent Orientation after Polar Addition to Dehydroheterocyclic Intermediates

6.4. Cycloadditions to Dehydroheterocyclic Intermediates


Chapter 7 Other Dehydroaromatic Intermediates

7.1. 1,3-Dehydroaromatic Intermediates

7.2. 1,4-Dehydroaromatic Intermediates

7.3. 1,2-Dehydroferrocene

7.4. 2,3-Dehydro-1,6-Methano-[10]annulene


Chapter 8 Cycloalkynes

8.1. Generation of Cycloalkynes

8.1.1. Generation of Cycloalkynes from 1-Halogenocycloalkenes

8.1.2. Generation of Cycloalkynes from 1,2-Dihalogenocycloalkenes

8.1.3. Generation of Cycloalkynes by Rearrangement of Cycloalkylidenehalogenocarbanions

8.1.4. Generation of Cycloalkynes Via 1,2-Bis-Diazocycloalkanes

8.1.5. Further Methods of Generating Cycloalkynes

8.2. Polar Additions to Cycloalkynes

8.3. Cycloadditions to Cycloalkynes

8.3.1. Diels-Alder Additions to Cycloalkynes

8.3.2. 1,3-Dipolar Additions to Cycloalkynes

8.4. Isomerization and Oligomerization of Cycloalkynes

8.5. Reactivity of the Cycloalkynes


Author Index

Subject Index


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© Academic Press 1967
1st January 1967
Academic Press
eBook ISBN:

About the Author

Reinhard W. Hoffmann

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