Stereoselectivity in the Fe(II)/Cu(II)-mediated Homolytic Decomposition of thecis- andtrans-Isomers of Pinane Hydroperoxide

2002 ◽  
Vol 31 (8) ◽  
pp. 830-831 ◽  
Author(s):  
H. E. B. Lempers ◽  
R. A. Sheldon ◽  
K. A. D. Swift
Keyword(s):  
Homolytic Decomposition

Evidence for homolytic decomposition of ammonium nitrate at high temperature

1989 ◽  
Vol 93 (10) ◽  
pp. 4029-4033 ◽  
Author(s):  
K. R. Brower ◽  
Jimmie C. Oxley ◽  
Mohan Tewari
Keyword(s):  
High Temperature ◽  
Ammonium Nitrate ◽  
Homolytic Decomposition

Homolytic decomposition of linoleic acid hydroperoxide: Identification of fatty acid products

Lipids ◽  
1974 ◽  
Vol 9 (9) ◽  
pp. 696-706 ◽  
Author(s):  
H. W. Gardner ◽  
R. Kleiman ◽  
D. Weisleder
Keyword(s):  
Fatty Acid ◽  
Linoleic Acid ◽  
Linoleic Acid Hydroperoxide ◽  
Homolytic Decomposition ◽  
Acid Hydroperoxide

Reactions of Chloramines with Ag(0) and Ag(I) States

1972 ◽  
Vol 50 (8) ◽  
pp. 1167-1180 ◽  
Author(s):  
O. E. Edwards ◽  
D. Vocelle ◽  
J. W. ApSimon
Keyword(s):  
Silver Oxide ◽  
Silver Ions ◽  
Silver Ion ◽  
Short Chain ◽  
Ferrous Ion ◽  
Metallic Silver ◽  
Nitrenium Ions ◽  
Homolytic Decomposition ◽  
Nitrogen Radicals ◽  
Silver Metal

Reactions of N-chloroazacyclooctane and N-chloroazacyclononane are described which give good yields of bicyclic amines. These are: (a) short chain homolytic reactions involving neutral nitrogen radicals initiated by ferrous ion or metallic silver; (b) apparent homogeneous reactions involving silver ion and bases; (c) reactions using silver oxide suspension which also require added bases.Both rate and product composition for (b) and (c) are sensitive to oxygen indicating that they are homolytic processes, probably initiated by traces of silver metal. No evidence for involvement of discrete nitrenium ions was found. However, reaction of N-chloroisoquinuclidine with silver ions has the character of a heterolytic process, giving products completely distinct from those from its homolytic decomposition. The addition of neutral piperidino radicals to styrene is described.

Formation of O? Centers by Homolytic Decomposition of OH? Groups on Magnesium Oxide

1975 ◽  
Vol 14 (8) ◽  
pp. 568-569 ◽  
Author(s):  
Friedemann Freund ◽  
N. Scheikh-ol-Eslami ◽  
Horst Gentsch
Keyword(s):  
Magnesium Oxide ◽  
Oh Groups ◽  
Homolytic Decomposition

Déplacements homolytiques intramoléculaires. 19. Stéréochimie de la décomposition induite de peroxydes insaturés conduisant à la formation d'hétérocycles à trois et quatre chaînons

1991 ◽  
Vol 69 (8) ◽  
pp. 1320-1325 ◽  
Author(s):  
X. Lubeigt ◽  
F. Flies ◽  
M. J. Bourgeois ◽  
E. Montaudon ◽  
B. Maillard
Keyword(s):  
Key Words ◽  
Homolytic Decomposition ◽  
Homolytic Substitution ◽  
C Nmr

Homolytic decomposition induced by addition of dichloromethyl radicals to β- and γ-unsaturated peroxides having a substituent on the chain linking the unsaturation and the peroxide function was studied. The stereochemistry of the heterocycles produced was determined by I3C NMR and the stereoselectivity of intramolecular homolytic substitution on the peroxidic bond discussed. Key words: unsaturated peroxides, homolytic intramolecular substitutions, radical additions, oxygenated heterocycles.

Effect of high pressure on the rate of homolytic decomposition of dicyclohexylperoxydicarbonate in the liquid phase

1984 ◽  
Vol 33 (11) ◽  
pp. 2262-2264
Author(s):  
V. M. Zhulin ◽  
T. V. Lipovich ◽  
V. L. Antonovskii
Keyword(s):  
High Pressure ◽  
Liquid Phase ◽  
Homolytic Decomposition

DFT mechanistic studies on the epoxidation of cyclohexene by non-heme tetraaza manganese complexes

2009 ◽  
Vol 87 (1) ◽  
pp. 33-38 ◽  
Author(s):  
Alicja Haras ◽  
Tom Ziegler
Keyword(s):  
Density Functional ◽  
Direct Transfer ◽  
Energy Landscapes ◽  
Olefin Epoxidation ◽  
Mechanistic Studies ◽  
Metal Centre ◽  
Functional Theory ◽  
Homolytic Decomposition ◽  
Experimental Findings ◽  
Epoxidation Of Cyclohexene

Herein, we report density functional calculations on the epoxidation of cyclohexene with H2O2 activated by (Me2EBC)MnCl2 (Me2EBC stands for 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). The computed energy landscapes for different interaction modes of cyclohexene with the MnIV-hydroperoxo complex and the MnV-oxo species support recent experimental findings by Busch and co-workers [J. Am. Chem. Soc. 127, 17170 (2005)], according to which the MnIV-hydroperoxo species is the active complex for olefin epoxidation. Thus, the dominant olefin epoxidation pathway is via direct transfer of the distal protonated oxygen of the hydroperoxo adduct without changes in the oxydation state of its tetravalent metal centre, i.e., the mechanism commonly observed in the uncatalyzed epoxidation by peracids. The homolytic decomposition of the O–OH bond in the active manganese complex leading to the MnV-oxo species is found to be the only epoxidation pathway that could possibly compete with the Oβ transfer from the hydroperoxo adduct. However, the generated MnV-oxo is shown to be a rather poor oxidant resulting in low yields of the target epoxy cyclohexane.Key words: epoxidation, density functional theory, permanganic acid, peracid.

Radical chain mechanism of the homolytic decomposition of organocobalt complexes

1991 ◽  
Vol 27 (3) ◽  
pp. 255-261 ◽  
Author(s):  
A. K. Yatsimirskii ◽  
I. Ya. Levitin ◽  
O. I. Kavetskaya ◽  
M. V. Tsikalova ◽  
V. I. Bakhmutov ◽  
...  
Keyword(s):  
Chain Mechanism ◽  
Radical Chain ◽  
Radical Chain Mechanism ◽  
Homolytic Decomposition
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