Superacids and Their Derivatives. V. Kinetics and Mechanism of the Cationic Polymerization of 3,3-Bis(chloromethyl)oxacyclobutane Initiated by Ethyl Trifluoromethanesulfonate. Evidence for Ester Type Propagating Species
スポンサーリンク
概要
- 論文の詳細を見る
Kinetic analysis of the cationic ring-opening polymerization of 3,3-bis(chloromethyl)oxacyclobutane (BCMO) initiated by ethyl trifluoromethanesulfonate (EtOSO<SUB>2</SUB>CF<SUB>3</SUB>) was carried out by direct determination of the instantaneous concentrations of monomer, initiator, and propagating species by means of <SUP>1</SUP>H and <SUP>19</SUP>F NMR spectroscopy. It was established that the polymerization of BCMO proceeds <I>via</I> an ester type propagating species (<B>4</B>). The propagating species of the first (P<SUB>1</SUB><SUP>*</SUP>) and subsequent propagations (P<I><SUB>n</SUB></I><SUP>*</SUP>, <I>n</I>≥2) were directly observed. The rate constants of initiation (<I>k</I><SUB>i</SUB>) and propagations of the first (<I>k</I><SUB>p1</SUB>), second (<I>k</I><SUB>p2</SUB>) and subsequent steps (<I>k</I><SUB>p<I>n</I></SUB>, <I>n</I>≥3) were determined. Activation parameters as well as the solvent effect supported the proposed mechanism, in which the rate-determining step is a dipole-dipole reaction between monomer and propagating ester species to form the intermediate cyclic oxonium ions (<B>7</B>, <B>8</B>, and <B>10</B>) as unstable transient species.
- 公益社団法人 日本化学会の論文
著者
-
Saegusa Takeo
Department Of Synthetic Chemistry Faculty Of Engineering Kyoto University
-
Kobayashi Shiro
Department Of Material Chemistry Graduate School Of Engineering Kyoto University
-
Danda Hidenori
Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University
関連論文
- Concomitant Cranial and Lumbar Subdural Hematomas : Case Report
- Rupture of a Vertebral Artery Dissecting Aneurysm Developing Immediately After Trapping of a Dissecting Aneurysm on the Contralateral Vertebral Artery : Case Report
- Intracerebral Hemorrhage Caused by a Neoplastic Aneurysm From Pleomorphic Lung Carcinoma
- Cervical Ligamentum Flavum Ossification
- Middle Cerebral Artery Thrombolysis Through the Contralateral Internal Carotid Artery : Case Report
- Multiple Immunostaining Methods to Detect Traumatic Axonal Injury in the Rat Fluid-Percussion Brain Injury Model
- Central neurocytoma expressing characteristics of ependymal differentiation : electron microscopic findings of two cases
- Ab Initio Calculation on the Reaction Mechanism of "Radical-Controlled" Oxidative Polymerization of Phenols
- Enzymatic Oxidative Polymerization of p-t-Butylphenol and Characterization of the Product Polymer
- High-Performance Immobilized Lipase Catalyst for Polyester Synthesis
- Lipase-Catalyzed Ring-Opening Polymerization of Substituted Lactones
- Structural Control in Enzymatic Oxidative Polymerization of Phenols with Varying the Solvent and Substituent Nature
- Enzymatic Synthesis of Polyesters in Ionic Liquids
- A New Crosslinking Method of Vinyl Polymers Having a Phenol Moiety via Oxidative Coupling
- Laccase-Catalyzed Curing of Vinyl Polymers Bearing a Phenol Moiety in the Side Chain
- Preparation of Artifical Urushi via an Environmentally Benign Process
- Lipase-Catalyzed Hydrolytic Degradation of Polyurethane in Organic Solvent
- Molecular Weight Control of Polyphenols by Enzymatic Copolymerization of Phenols
- Artificial Urushi: Design, Synthesis, and Enzymatic Curing of New Urushiol Analogues
- Synthesis and Curing of Crosslinkable Polyphenols from Urushiol Analogues
- Enzymatic Synthesis and Curing of Poly (cardanol)
- リパーゼ
- Group Transfer Polymerization of Methacryl-Type Poly(2-oxazoline) Macromonomers
- Enzymatic Synthesis of Aromatic Polyesters by Lipase - Catalyzed Polymerization of Dicarboxylic Acid Divinyl Esters and Glycols
- Reactivity in Radical Polymerization of Poly(2 - oxazoline) Macromonomers
- Enzymatic Polymerization of Dicarboxylic Acid and Glycol to Polyester in Solvent-Free System
- Peroxidase-Catalyzed Dispersion Polymerization of Phenol Derivatives
- Extremely Efficient Catalysis of Immobilized Lipase in Ring-opening Polymerization of Lactones
- Mechanistic Studies on the Lipase-Catalyzed Ring-Opening Polymerization of Lactones
- Novel Bienzymatic Catalysis System for Oxidative Polymerization of Phenols
- Dehydration Polymerization in Aqueous Medium Catalyzed by Lipase
- Lipase - Catalyzed Ring - Opening Polymerization and Copolymerization of β - Propiolactone
- Enzymatic Synthesis and Thermal Properties of a New Class of Polyphenol
- Peroxidase-Catalyzed Oxidative Polymerization of Cresols to a New Family of Polyphenols
- One-Shot Synthesis of Polyester Macromonomer by Enzymatic Ring-Opening Polymerization of Lactone in the Presence of Vinyl Ester
- Preparation of Polyphenol Particles by Dispersion Polymerization Using Enzyme as Catalyst
- Immobilized Lipase Showing High Catalytic Activity toward Enzymatic Ring-Opening Polymerization of Macrolides
- Persistent Primitive Trigeminal Artery Aneurysm Associated With Cerebellar Hemangioblastoma : Case Report
- Using Case-Based Reasoning for Collaborative Learning System on the Internet (Special Issue on Educational System using Multimedia and Communication Technology)
- A Collaborative Learning Support System for Systems Design
- Regioselective Polymerization of Sorbitol and Divinyl Sebacate Using Lipase Catalyst
- Synthesis of Aliphatic Polyester by Insertion of Glycols into Polyanhydrides Using Lipase Catalyst
- Enzymatic Oxidation Polymerization of ο-Phenylenediamine
- Antioxidant Polymer Particles, Enzymatic Immobilization of Catechin on Polymer Particles
- Enzymatic Synthesis and Antioxidant Property of Poly(allylamine)-Catechin Conjugate
- Thermoresponsive Hydrogels Based on Biodegradable Poly(amino acid)s
- Enzymatic Ring-Opening Polymerization of Lactones to Polyesters by Lipase Catalyst: Unusually High Reactivity of Macrolides
- Enzymatic Template Polymerization of Phenol in the Presence of Water-soluble Polymers in an Aqueous Medium
- Enzymatic Polymerization for Precision Polymer Synthesis
- Enzymatic Ring-Opening Polymerization of Lactones Catalyzed by Lipase
- Enantioseparation by Using Chitin Phenylcarbamates as Chiral Stationary Phases for High-Performance Liquid Chromatography
- Man-made urushi : Preparation of crosslinked polymeric films from renewable resources via air-oxidation processes
- Precise Structure Control of Enzymatically Synthesized Polyphenols
- Guaiacol Oxidation Products in the Enzyme-Activity Assay Reaction by Horseradish Peroxidase Catalysis
- Enzymatic Synthesis of Soluble Polyphenol
- Chemical Reaction at Specific Sites and Reaction-induced Self-assembly : Enzymatic Polymerization of Cellulose As a Problem in Open-Nonequilibrium Phenomena
- Lipase-catalyzed ring-opening polymerization of 16-hexadecanolide
- Synthesis of a New Family of Phenol Resin by Enzymatic Oxidative Polymerization
- A Novel Method for Synthesis of Cellooligosaccharide Derivatives by Using Enzyme Catalyst
- Selective Posterior Decompression of the Cervical Spine
- Posttraumatic Carotid-Cavernous Fistulae Treated by Internal Carotid Artery Trapping and High-Flow Bypass Using a Radial Artery Graft : Two Case Reports
- Spectroscopic Study on Direction and Inclination of Helical Peptides in Monolayers Formed at the Air/Water Interface and on a Gold Substrate
- Photocurrent Generation by the Self-Assembled Monolayers Interating a Photoenergy-Harvesting System and an Electron-Transport System of Helical Peptide
- Preparation of Monodisperse Poly(N-vinylformamide) Particles by Dispersion Polymerization in Methanol Solvent
- Lipase-Catalyzed Polymerization of Divinyl Adipate with Glycols to Polyesters
- Anionic Ring-Opening Polymerization of 1,2,2-Trimethyl-1-phenyl-1,2-disilacyclopentane
- Amino Silica Gels Acting as a Carbon Dioxide Absorbent
- Isomerization Polymerization of 2-Oxazoline. I. Preparation of Unsubstituted 2-Oxazoline Polymer
- Resection of Arteriovenous Malformation in a Patient With Hemophilia Type A
- Enzymatic Synthesis of Alternatingly 6-O-Carboxymethylated Chitotetraose by Selective Glycosidation with Chitinase Catalysis
- Enzymatic Polymerization to an Alternating N-Phthaloyl Chitin Derivative Catalyzed by Chitinase
- Chitinase-Catalyzed Copolymerization to a Chitin Derivative Having Glucosamine Unit in Controlled Proportion
- Effect of Fluorine Substituent on the Chitinase-catalyzed Polymerization of Sugar Oxazoline Derivatives
- A case of psychotic disorder associated with a right temporal lesion : A special reference to magnetic resonance imaging and single photon emission computed tomography findings
- Detailed Study of Graft Sinking and Worsening of the Fused Segment Angle in Patients With Cervical Disease Treated With the Williams-Isu Method
- Emulsion Copolymerization of Styrene with Amphiphilic Poly(2-oxazoline) Macromonomer
- Lipase-Catalyzed Ring-Opening Polymerization of Cyclic Diesters
- A Novel Thermo-Sensitive Polymer. Poly(2-iso-propyl-2-oxazoline)
- Prepartion of Reactive Monodisperse Particles in the Micron Range by Dispersion Polymerization of Glycidyl Methacrylate
- Ring-Opening Glycosylation of a Chitobiose Oxazoline Catalyzed by a Non-Chitinolytic Mutant of Chitinase
- Enzymatic Synthesis of 3-O-Methylated Chitin Oligomers from New Derivatives of a Chitobiose Oxazoline
- Synthesis of Polygermanes by Ligand Substitution Polymerization of the 1, 4-Dioxane Complex of Germanium Dichloride with Organolithium Compounds
- The First Synthesis of Bisgermylene and Bisstannylene with Acyclic Structure
- Copolymerization of Germylene with Acetylene Monomers by Rhodium Catalysis
- Dissecting Aneurysm of the Anterior Temporal Artery : Case Report
- Addition reaction of carboxylic anhydrides to the carbon-nitrogen double bond of unsubstituted cyclic imidates.
- Reactions of Nitrogen Oxides with Isocyanide
- Facile synthesis of 2-phenyl-1,2-oxaphospholane and its related new compounds. The family of deoxophostones and deoxothiolphostones.
- Indole syntheses utilizing o-methylphenyl isocyanides.
- The Acid-catalyzed Reaction of Isocyanide with Oxetane
- Superacids and Their Derivatives. III. Kinetics of the Oxonium Ion Formation from Superacid Esters and Tetrahydropyran. Oxonium-Ester Equilibria
- Superacids and Their Derivatives. V. Kinetics and Mechanism of the Cationic Polymerization of 3,3-Bis(chloromethyl)oxacyclobutane Initiated by Ethyl Trifluoromethanesulfonate. Evidence for Ester Type Propagating Species
- Synthetic Reactions by Complex Catalysts. XXIV. A New Catalyst of Copper-Isocyanide Complex for the Michael Addition
- Synthetic Reactions by Complex Catalysts. XVI. The Dimerization of Acrylonitrile and Acrylate by Means of the Metal-Isocyanide Complex
- The Thermal Rearrangement and Degradation of 2,3-Bis(alkylimino)oxetane
- Synthesis of indole derivatives by Cu2O-catalyzed cyclization of o-(.ALPHA.-cyanoalkyl)phenyl isocyanides and o-[.ALPHA.-(methoxycarbonyl)alkyl]phenyl isocyanides.
- Synthetic Reactions by Complex Catalysts. XXVI. The Copper-catalyzed Reaction of α,β-Unsaturated Isocyanide with Active Methylene Compounds
- Synthetic Reactions by Complex Catalysts. XXV. The Copper-catalyzed Reaction of Allyl Isocyanide with Carbonyl Compounds and Olefins. Syntheses of 4-Vinyl-2-oxazoline and 5-Vinyl-1-pyrroline Derivatives
- Synthetic Reactions by Complex Catalysts XXVIII. Reaction of β-Propiolactone with Alkyl Halide Caused by Cu2O-Isonitrile Complex
- Kinetic Studies on the Cationic Ring-Opening Polymerization of Tetrahydrofuran Initiated by Superacid Esters