ESR study of radical halogen abstractions. Participation of electron-transfer mechanism in the radical halogen abstractions.
スポンサーリンク
概要
- 論文の詳細を見る
The halogen-abstraction reactions of carbon radicals were investigated as a model of the chain-transfer reaction in the radical polymerization of vinyl compounds. The kinetics of the halogen-abstraction reaction of carbon radicals ((CH<SUB>3</SUB>)<SUB>2</SUB>\dotCX, X=OC<SUB>6</SUB>H<SUB>5</SUB>, OCOCH<SUB>3</SUB>, SC<SUB>6</SUB>H<SUB>5</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>, and CN) from tetrahalomethanes(CBr<SUB>4</SUB>, CBrCl<SUB>3</SUB>, CCl<SUB>4</SUB>) were studied in toluene at 80 °C by the ESR method using 2-(<I>t</I>-butyl)thioacrylonitrile as a spin-trapping reagent. The reactivity of these radicals for each halomethane decreased in the order X: OC<SUB>6</SUB>H<SUB>5</SUB>>OCOCH<SUB>3</SUB>>SC<SUB>6</SUB>H<SUB>5</SUB>>C<SUB>6</SUB>H<SUB>5</SUB>>CN The reactivity of tetrahalomethanes for each radical decreased in the order CBr<SUB>4</SUB>>CBrCl<SUB>3</SUB>>CCl<SUB>4</SUB>. Results are explained by taking into account the electron-transfer process from carbon radicals to tetrahalomethanes. Absolute rate constants of the halogen abstraction of (CH<SUB>3</SUB>)<SUB>2</SUB>\dotCCN and (CH<SUB>3</SUB>)<SUB>2</SUB>\dotCC<SUB>6</SUB>H<SUB>5</SUB> from CBr<SUB>4</SUB> and CBrCl<SUB>3</SUB>, and of their additions to 2-(<I>t</I>-butylthio)acrylonitrile were estimated by the spin-trapping method, and they were compared with available data for similar reactions.
- 公益社団法人 日本化学会の論文
著者
-
Hayashi Koichiro
Institute For Human Science And Biomedical Engineering National Institute Of Advanced Industrial Sci
-
Kamachi Mikiharu
Department of Macromolecular Chemistry, Faculty of Science, Osaka University
-
Kuwae Yoko
Department of Macromolecular Science, Faculty of Science, Osaka University
-
Viehe Heinz
Laboratory of Organic Chemistry, University of Louvain
-
Kuwae Yoko
Department of Macromolecular Chemistry, Faculty of Science, Osaka University
関連論文
- Effect of Low-Intensity Aerobic Exercise Training on Arterial Compliance in Postmenopausal Women
- THE EFFECTS OF DAILY PHYSICAL ACTIVITY ON THE AGE-RELATED CAROTID ARTERIA STIFFENING IN MIDDLE-AGED AND ELDERLY PEOPLE(Proceedings of The 8^ Asian Federation of Sports Medicine Congress 2005 Tokyo)
- Effect of Systemic Nitric Oxide Synthase Inhibition on Arterial Stiffness in Humans
- Magnetic Properties of Organic Radical Magnets,MOTMP,MATMP and AOTMP
- Low Temperature Magnetic Properties of Organic Radical Magnet, MOTMP
- Relationship of Muscle Strength with Dehydroepiandrosterone Sulfate(DHEAS),Testosterone and Insulin-like Growth Factor-I in Male and Female Athletes
- Radical Polymerization of 5-(4'-Acrylamidophenyl)-10,15,20-triphenylporphine and 5-(4'-Methacrylamidophenyl)-10,15,20-triphenylporphine
- Polymerization of n-Butyl Vinyl Ether Photoinitiated by the Initiator System Poly (methyl phenyl silane)/N-Ethoxy-2-methylpyridinium Iodide/ZnI_2/Benzaldehyde
- Study on the Mechanism of the Cationic Polymerization of Cyclohexene Oxide Initiated by the Photosystem of Poly(methyl phenyl silane)and Pyridinium Salts
- Preparation and Chemical Reactions of Trifluoroacetaldegyde Azine (1,1,1,6,6,6-Hexafluoro-3,4-deaza-2,4-hexadiene)
- Radical Polymerization of 5-(4-Acrylamido)-phenyl-10, 15, 20-triphenylporphyrin
- Effects of Aerobic Exercise Training on the Stiffness of Central and Peripheral Arteries in Middle-Aged Sedentary Men
- Brachial-Ankle Pulse Wave Velocity : A New Index of Central Arterial Stiffness? (Atherosclerosis, Basic 7 (IHD), The 69th Annual Scientific Meeting of the Japanese Circulation Society)
- P2-24 Changes in arterial stiffness with endurance training : differences by arterial locus(The Proceedings of the 12th Annual Meetings of Japan Society of Exercise and Sports Physiology)
- DO SERUM IGF-I AND IGFBP-3 LEVELS REFLECT THE INCREMENT OF BONE MASS THROUGH RUNNING TRAINING IN FEMALE RATS?
- Site-Selective Complexation of Amphiphilic Compounds by Cyclodextrins
- Preparation and Characterization of Inclusion Complexes of Poly(alkyl vinyl ether) with Cyclodextrins
- Complex Formation of Cyclodextrins with Cationic Polymers
- Syntheses and Properties of π-Conjugated Polymers Containing Chromophore.2.Introduction of Porphyrin Units into Main Chain of Water-Soluble Small Band Gap Polymer
- Syntheses and Properties of π-Conjugated Polymers Containing Chromophore. 1. Water-Soluble Small-Bandgap Polymer Backbone
- Electron Spin Resonance Spectroscopic Pursuit of Network Formation Processes in Free-Radical Crosslinking Polymerizations I. Microscopic Environmental Evaluation around Copper(II) Tetraphenylporphyrin Spin Probe Incorporated into or Excluded from Polymer
- Synthesis of Novel π-Conjugated Polymer Containing Porphyrins
- Enormously Long Triplet Lifetime of Zinc(II) Tetraphenylporphyrin Incorporated As a Pendant of a Liquid Crystalline Polymethacrylate Based on Cholesterol Mesogens
- Imaging Antibody Molecules at Room Temperature by Contact Mode Atomic Force Microscope
- Anomalous Behavior of Triplet-Excited Zinc(II) Tetraphenylporphyrin Moieties Compartmentalized in the Hydrophobic Cluster of Pendant Cyclododecyl Groups in an Amphiphilic Polyelectrolyte
- Lattice Matching of α-Cyclodextrin Commensurate with Molybdenum Disulfide Studied by Scanning Tunneling Microscopy
- Association between the Ventilatory Treshold and the Break-point in the Heart Rate/Work Rate Relationship: Comparison with the Break-point in the Double Product/Work Rate
- Intramolecular dimer and excimer phosphorescence of poly(2-vinylnaphthalene) and copolymers of 2-vinylnaphthalene and phenyl vinyl ketone.
- Intramolecular Energy Transfer in Covalently Linked Polypyridine Ruthenium(II)/Osmium(II) Binuclear Complexes. Ru(II)(bpy)2Mebpy-(CH2)n-MebpyOs(II)(bpy)2 (n=2, 3, 5, and 7).
- Novel Coulombic Complexes of Amphiphilic Polyelectrolytes and Double-chain Surfactants.
- ESR studies on chain transfer reactions: Rate constants for the reactions of model radicals of polystyrene growing chain ends with tetrahalomethanes and thiophenols.
- Laser flash photolysis of azocumenes. Direct observation of stepwise decomposition.
- Physicochemical properties of polyacrylates containing tetraphenyl-prophinatocobalt(II) and chloro(tetraphenyl-porphinato)iron(III) as side chains.
- ESR study of radical halogen abstractions. Participation of electron-transfer mechanism in the radical halogen abstractions.
- Macromolecular Recognition. Formation of Inclusion Complexes of Polymers with Cyclodextrins.:Formation of Inclusion Complexes of Polymers with Cyclodextrins