Thermal Decomposition oft-Butyl 3,3,3-Triarylperpropionates. Evidence for the Intramolecular Rearrangement and Cyclization of Aliphatic Acyloxy Radicals

1963 ◽  
Vol 85 (22) ◽  
pp. 3708-3709 ◽  
Author(s):  
W. H. Starnes
Keyword(s):  
Thermal Decomposition ◽  
Intramolecular Rearrangement

Thermal Decomposition of N-Acyloxy-N-alkoxyamides - a New HERON Reaction

2010 ◽  
Vol 63 (12) ◽  
pp. 1717 ◽  
Author(s):  
Jennifer P. Johns ◽  
Arjan van Losenoord ◽  
Clément Mary ◽  
Pierre Garcia ◽  
Damian S. Pankhurst ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Substituent Effects ◽  
Intramolecular Rearrangement ◽  
Nitrate Ester ◽  
Solvent Cage ◽  
Amide Resonance

The HERON reaction has been observed in the thermal decompositions of N-acyloxy-N-alkoxyamides 1b, members of the class of anomeric amides. The N,N-bisoxo-substitution results in reduced amide resonance and this, combined with an nO–σ*NOAcyl anomeric destabilization of the N–OAcyl bond, results in their intramolecular rearrangement to anhydrides 42 and alkoxynitrenes 43 in competition with homolysis of the N–OAcyl bond to alkoxyamidyls 51. The primary HERON product alkoxynitrenes are scavenged by oxygen, giving a nitrate ester, in competition with a rearrangement to nitriles and dimerization to hyponitrites, leading, under the conditions, to alcohols and aldehydes. Persistent alkoxyamidyls most likely form a 1,3-diradical in a solvent-cage reaction, which cyclizes to 3,5-disubstituted-(5H)-1,4,2-dioxazoles 47. Substituent effects support this competition reaction.

scholarly journals A study of the chain reaction in the thermal decomposition of diethyl ether.

1938 ◽  
Vol 167 (931) ◽  
pp. 456-463 ◽  
Author(s):  
J. E. Hobbs ◽  
Cyril Norman Hinshelwood
Keyword(s):  
Thermal Decomposition ◽  
Diethyl Ether ◽  
Reaction Rate ◽  
Initial Rate ◽  
Intramolecular Rearrangement ◽  
Chain Mechanism ◽  
Chain Reaction ◽  
Experimental Conditions ◽  
Rearrangement Process ◽  
A Chain

In a recent paper (Hobbs and Hinshelwood 1938), information about the chain mechanisms involved in the thermal decomposition of ethane was obtained by studying the variation with the ethane concentration of the shape of the curve which represents in the reaction rate as a function of minute quantities of added nitric oxide. This paper describes the results of a similar investigation carried out with diethyl ether, the behaviour of which shows an interesting contrast with that of ethane. The thermal decomposition of diethyl ether in the neighbourhood of 500° C. occurs partly by a chain mechanism in which free radicals are formed, and partly by intramolecular rearrangement (Staveley and Hinshelwood 1936, 1937). The end- products of the decomposition are methane, ethane, and carbon monoxide, with small amounts of hydrogen and unsaturated substances. Acetaldehyde is an intermediate product formed either in the rearrangement process, or, as in the mechanism put formed below, during the chain reaction (Fletcher and Rollefson 1936). The acetaldehyde, however, decomposes rapidly under the experimental conditions and the initial rate is sensibly that of the decomposition of the ether into final products.

Applications of Photoelectron Microscopy

1976 ◽  
Vol 34 ◽  
pp. 506-507
Author(s):  
William J. Baxter
Keyword(s):  
Electron Microscopy ◽  
Thermal Decomposition ◽  
Chemical Composition ◽  
Ultraviolet Radiation ◽  
Thin Layer ◽  
Edge Effects ◽  
Electron Optics ◽  
Surface Layers ◽  
Crystalline Orientation ◽  
Fluorescent Screen

In this form of electron microscopy, photoelectrons emitted from a metal by ultraviolet radiation are accelerated and imaged onto a fluorescent screen by conventional electron optics. image contrast is determined by spatial variations in the intensity of the photoemission. The dominant source of contrast is due to changes in the photoelectric work function, between surfaces of different crystalline orientation, or different chemical composition. Topographical variations produce a relatively weak contrast due to shadowing and edge effects.Since the photoelectrons originate from the surface layers (e.g. ∼5-10 nm for metals), photoelectron microscopy is surface sensitive. Thus to see the microstructure of a metal the thin layer (∼3 nm) of surface oxide must be removed, either by ion bombardment or by thermal decomposition in the vacuum of the microscope.

Preparation and characterisation of vanadium pentoxide supported rhodium catalyst

1988 ◽  
Vol 46 ◽  
pp. 946-947
Author(s):  
A. Legrouri
Keyword(s):  
Aqueous Solution ◽  
Thermal Decomposition ◽  
Physicochemical Properties ◽  
Surface Area ◽  
Vanadium Pentoxide ◽  
High Purity ◽  
Gas Adsorption ◽  
Rhodium Catalyst ◽  
Optical Methods ◽  
Reducible Oxides

The industrial importance of metal catalysts supported on reducible oxides has stimulated considerable interest during the last few years. This presentation reports on the study of the physicochemical properties of metallic rhodium supported on vanadium pentoxide (Rh/V2O5). Electron optical methods, in conjunction with other techniques, were used to characterise the catalyst before its use in the hydrogenolysis of butane; a reaction for which Rh metal is known to be among the most active catalysts.V2O5 powder was prepared by thermal decomposition of high purity ammonium metavanadate in air at 400 °C for 2 hours. Previous studies of the microstructure of this compound, by HREM, SEM and gas adsorption, showed it to be non— porous with a very low surface area of 6m2/g3. The metal loading of the catalyst used was lwt%Rh on V2Q5. It was prepared by wet impregnating the support with an aqueous solution of RhCI3.3H2O.

Observations of the Thermal Decomposition of Brucite

1968 ◽  
Vol 26 ◽  
pp. 446-447
Author(s):  
P. L. Burnett ◽  
W. R. Mitchell ◽  
C. L. Houck
Keyword(s):  
Thermal Decomposition ◽  
Magnesium Oxide ◽  
Basal Plane ◽  
Magnesium Ions ◽  
A Value ◽  
Reaction Proceeds

Natural Brucite (Mg(OH)2) decomposes on heating to form magnesium oxide (MgO) having its cubic ﹛110﹜ and ﹛111﹜ planes respectively parallel to the prism and basal planes of the hexagonal brucite lattice. Although the crystal-lographic relation between the parent brucite crystal and the resulting mag-nesium oxide crystallites is well known, the exact mechanism by which the reaction proceeds is still a matter of controversy. Goodman described the decomposition as an initial shrinkage in the brucite basal plane allowing magnesium ions to shift their original sites to the required magnesium oxide positions followed by a collapse of the planes along the original <0001> direction of the brucite crystal. He noted that the (110) diffraction spots of brucite immediately shifted to the positions required for the (220) reflections of magnesium oxide. Gordon observed separate diffraction spots for the (110) brucite and (220) magnesium oxide planes. The positions of the (110) and (100) brucite never changed but only diminished in intensity while the (220) planes of magnesium shifted from a value larger than the listed ASTM d spacing to the predicted value as the decomposition progressed.

A magnetic super lattice

1987 ◽  
Vol 45 ◽  
pp. 360-361 ◽  
Author(s):  
M.D. Bentzon ◽  
J. v. Wonterghem ◽  
A. Thölén
Keyword(s):  
Thermal Decomposition ◽  
Oleic Acid ◽  
Magnetic Fluid ◽  
Magnetic Particles ◽  
Carbon Film ◽  
Thick Layer ◽  
Amorphous Iron ◽  
Super Lattice ◽  
Carrier Liquid ◽  
Median Diameter

We report on the oxidation of a magnetic fluid. The oxidation results in magnetic super lattice crystals. The “atoms” are hematite (α-Fe2O3) particles with a diameter ø = 6.9 nm and they are covered with a 1-2 nm thick layer of surfactant molecules.Magnetic fluids are homogeneous suspensions of small magnetic particles in a carrier liquid. To prevent agglomeration, the particles are coated with surfactant molecules. The magnetic fluid studied in this work was produced by thermal decomposition of Fe(CO)5 in Declin (carrier liquid) in the presence of oleic acid (surfactant). The magnetic particles consist of an amorphous iron-carbon alloy. For TEM investigation a droplet of the fluid was added to benzine and a carbon film on a copper net was immersed. When exposed to air the sample starts burning. The oxidation and electron irradiation transform the magnetic particles into hematite (α-Fe2O3) particles with a median diameter ø = 6.9 nm.

Supersonic jet spectrometry of chemical species resulting from thermal decomposition of polystyrene and polycarbonate

1992 ◽  
Vol 64 (19) ◽  
pp. 931A-940A ◽  
Author(s):  
Totaro Imasaka ◽  
Masami Hozumi ◽  
Nobuhiko Ishibashi
Keyword(s):  
Thermal Decomposition ◽  
Supersonic Jet ◽  
Chemical Species

Influence of thermal decomposition behavior of titanium precursors on (Ba,Sr)TiO3 thin films

2001 ◽  
Vol 11 (PR3) ◽  
pp. Pr3-675-Pr3-682 ◽  
Author(s):  
Y. S. Min ◽  
Y. J. Cho ◽  
D. Kim ◽  
J. H. Lee ◽  
B. M. Kim ◽  
...  
Keyword(s):  
Thin Films ◽  
Thermal Decomposition ◽  
Thermal Decomposition Behavior ◽  
Decomposition Behavior
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