Olefin Metathesis and Metathesis Polymerization
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Table of contents
- Contentsv
- Prefacexiii
- Abbreviationsxv
- Chapter 1. Introduction1
- 1.1 The olefin metathesis reaction1
- 1.2 Brief history5
- 1.3 The metal carbene mechanism7
- 1.4 Equilibria and stereoselectivity9
- Chapter 2. Survey of catalyst systems12
- 2.1 Introduction12
- 2.2 Group IVA19
- 2.3 Group VA21
- 2.4 Group VIA24
- 2.5 Group VIIA36
- 2.6 Group VIII40
- 2.7 Photochemically activated catalysts44
- Chapter 3. The metal carbene/metallacyclobutane mechanism50
- 3.1 Introduction50
- 3.2 Evidence from cross-metathesis reactions51
- 3.3 Evidence from the stereochemistry of metathesis of internal olefins52
- 3.4 Evidence from ring-opening metathesis polymerization (ROMP)54
- 3.5 Evidence from the reactions of well-defined metal carbene complexes58
- 3.6 Evidence from the reactions of metallacyclobutane complexes71
- 3.7 Evidence of initiating species in systems with non-carbene catalysts76
- 3.8 Theoretical treatments78
- Chapter 4. Related reactions82
- 4.1 Introduction82
- 4.2 [2 + 2] reactions between compounds containing multiple bonds82
- 4.3 Relationship to Ziegler–Natta polymerization86
- 4.4 Involvement of three-membered ring compounds in metathesis reactions90
- Chapter 5. Ethene and terminal alkenes92
- 5.1 Introduction92
- 5.2 Ethene92
- 5.3 Propene93
- 5.4 But-1-ene and its derivatives106
- 5.5 Pent-1-ene and its derivatives108
- 5.6 Hex-1-ene and its derivatives109
- 5.7 Higher acyclic terminal alkenes110
- Chapter 6. Acyclic disubstituted and trisubstituted ethenes116
- 6.1 Introduction116
- 6.2 Cis/trans isomerization116
- 6.3 Pent-2-ene and 4-substituted derivatives118
- 6.4 Hex-2-ene and 4-methylhex-2-ene120
- 6.5 Hept-2-ene and hept-3-ene120
- 6.6 Higher acyclic internal olefins121
- 6.7 Stereoselectivity in the metathesis of acyclic olefins122
- 6.8 1,1-Disubstituted olefins131
- 6.9 Trisubstituted ethenes133
- Chapter 7. Acyclic functionalized alkenes134
- 7.1 Introduction134
- 7.2 Esters135
- 7.3 Other carbonyl-containing compounds141
- 7.4 Ethers141
- 7.5 Amines142
- 7.6 Nitriles144
- 7.7 Chlorides and bromides145
- 7.8 Sulfides and sulfonates145
- 7.9 Silanes and germanes145
- 7.10 Phosphanes147
- Chapter 8. Acyclic dienes148
- 8.1 Introduction148
- 8.2 Double bonds linked only by C atoms149
- 8.3 Double bonds linked by C and Si, Ge or Sn atoms153
- 8.4 Double bonds linked by C and N atoms158
- 8.5 Double bonds linked by C and O atoms160
- 8.6 Double bonds linked by C and P atoms163
- 8.7 Double bonds linked by C and S atoms165
- 8.8 Double bonds linked by C, Si, and O, or C, B and O atoms165
- 8.9 Divinylferrocene165
- 8.10 Some further applications in organic synthesis165
- 8.11 Copolymers by metathesis condensation168
- Chapter 9. Cross-metathesis between acyclic compounds171
- 9.1 Introduction171
- 9.2 Ethene173
- 9.3 Propene173
- 9.4 Butenes173
- 9.5 Pentenes176
- 9.6 Hexenes178
- 9.7 Higher olefins181
- 9.8 Functionalized olefins184
- Chapter 10. Acetylenes190
- 10.1 Introduction190
- 10.2 Metathesis reactions involving total cleavage of the C=C bond192
- 10.3 Metathesis reactions involving cleavage of two of the three C=C bonds200
- 10.4 Metathesis reactions of enynes and dienynes221
- 10.5 Other metathesis routes to polyacetylenes222
- Chapter 11. Ring-opening metathesis polymerization: general aspects224
- 11.1 Introduction224
- 11.2 Thermodynamic aspects224
- 11.3 Efficiency of initiation232
- 11.4 The use of chain-transfer agents235
- 11.5 Molecular weight distributions237
- 11.6 Polymer microstructure238
- Chapter 12. Monocyclic alkenes and polyenes260
- 12.1 Introduction260
- 12.2 Four-membered rings260
- 12.3 Five-membered rings264
- 12.4 Six-membered rings270
- 12.5 Seven-membered rings271
- 12.6 Eight-membered rings272
- 12.7 Nine-membered tings281
- 12.8 Ten-membered tings282
- 12.9 Twelve-membered and other tings282
- Chapter 13. Polycyclic alkenes288
- 13.1 Introduction288
- 13.2 Monomers containing a fused cyclobutene ring288
- 13.3 Monomers containing a fused cyclopentene ring and one double bond293
- 13.4 Monomers containing a fused cyclopentene ring and more than one double bond316
- 13.5 Bicyclo[2.2.1] compounds containing heteroatoms in the ring system331
- 13.6 Other bicyclic compounds337
- Chapter 14. Copolymers of cycloalkenes340
- 14.1 Introduction340
- 14.2 Direct metathesis copolymerization340
- 14.3 Cyclic co-oligomers345
- 14.4 Block copolymers by sequential addition of monomers to living systems346
- 14.5 Block copolymers by modification of homopolymers353
- 14.6 Comb and graft copolymers356
- 14.7 Copolymers by ROMP in conjunction with radical reactions357
- Chapter 15. Cross-metathesis between cyclic and acyclic olefins358
- 15.1 Introduction358
- 15.2 End-groups and telomers358
- 15.3 Dependence of molecular weight on [M2]/[M1]365
- 15.4 Kinetic data368
- Chapter 16. Degradation of unsaturated polymers by metathesis375
- 16.1 Introduction375
- 16.2 Degradation by intramolecular metathesis376
- 16.3 Degradation by intermolecular metathesis379
- Chapter 17. Applications of the olefin metathesis reaction397
- 17.1 Introduction397
- 17.2 The Phillips triolefin process397
- 17.3 The neohexene process398
- 17.4 The Shell Higher Olefins Process400
- 17.5 Other multistage processes involving metathesis402
- 17.6 The isoamylene process404
- 17.7 a,ω-Diolefins404
- 17.8 trans-Poly(1-pentenylene)405
- 17.9 trans-Poly(1-octenylene)406
- 17.10 Polymers of norbornene407
- 17.11 Polymers of norbornene derivatives407
- 17.12 Miscellaneous410
- Bibliography411
- Index461
This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis.
Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials science and chemical engineering.
Key Features
* Discusses different classes of olefin metathesis and the choice of reaction conditions and catalyst
* Considers commercial processes with examples from existing and new technologies
* Provides a complete overview of the subject from its beginning to the present day
Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials science and chemical engineering.
Key Features
* Discusses different classes of olefin metathesis and the choice of reaction conditions and catalyst
* Considers commercial processes with examples from existing and new technologies
* Provides a complete overview of the subject from its beginning to the present day