Thiyl Radicals. II. Reactions of meso-Substituted Anthracene Derivatives with Oxygen and Mercaptoacetic Acid

1963 ◽  
Vol 16 (5) ◽  
pp. 845 ◽  
Author(s):  
ALJ Beckwith ◽  
LB See
Keyword(s):  
Acetic Acid ◽  
Free Radical ◽  
Hydrogen Atom ◽  
Alkyl Substituent ◽  
Mercaptoacetic Acid ◽  
Hydrogen Atom Abstraction ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Thiyl Radicals ◽  
Anthracene Derivatives

9-Methyl- and 9-benzylanthracene each react readily with mercaptoacetic acid and oxygen in benzene yielding (9-methyl-10-anthry1thio)acetic acid and(9-benzyl-10-anthry1thio)acetic acid respectively. There is no evidence for hydrogen atom abstraction from the alkyl substituent by free thiyl radicals. 9,10-Dimethylanthracene, when similarly treated, affords α-(carboxymethylthio)-9,10-dimethylanthracene, but 9,10-diphenylanthracene remains unaffected. These results are consistent with the free-radical-chain mechanism previously suggested.1

Synthetic application of α-hydroxydiazene systems. I. Esters from radical chain reactions of unsaturated compounds with 2-hydroxy-2,5,5-trimethyl-Δ3-1,3,4-oxadiazoline

1976 ◽  
Vol 54 (9) ◽  
pp. 1341-1344 ◽  
Author(s):  
Peter Knittel ◽  
John Warkentin
Keyword(s):  
Free Radical ◽  
Hydrogen Atom ◽  
Multiple Bond ◽  
Hydroxyl Group ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Stable Free Radical ◽  
Chain Reactions ◽  
Unsaturated Compounds ◽  
Synthetic Application

2-Hydroxy-2,5,5-trimethyl-Δ3-1,3,4-oxadiazoline (1) reacts with acetylenic and olefinic unsaturated systems by addition of the 2-acetoxy-2-propyl group and a hydrogen atom, respectively, to the two atoms forming the multiple bond. The regiochemistry of addition to unsymmetric unsaturated systems is that predicted for a radical chain mechanism, in which the 2-acetoxy-2-propyl radical adds to the multiple bond so as to form the more stable free radical which then abstracts a hydrogen atom from the hydroxyl group of 1. Polymerization of the unsaturated substrate, as well as abstraction of allylic hydrogen (if any) are competing processes. Yields of adducts, based on 1, ranged from 80% in reaction with crotonaldehyde to 10% in reaction with cyclohexene.

Metal ion initiated halogenation reaction of N-haloamines

1970 ◽  
Vol 48 (4) ◽  
pp. 544-545 ◽  
Author(s):  
F. Minisci ◽  
G. P. Gardini ◽  
F. Bertini
Keyword(s):  
Free Radical ◽  
Radical Cation ◽  
Chlorine Atom ◽  
Metal Ion ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Radical Chain Mechanism ◽  
Halogenation Reaction ◽  
Amino Radical Cation ◽  
Methyl Heptanoate

The metal ion catalyzed chlorination of 1-chlorobutane, 1-chlorohexane, methyl-pentanoate, and methyl-heptanoate by protonated N-chloroamines proceeds by a free radical chain mechanism and the chain carrying species was shown not to be a chlorine atom, but an amino radical cation.

The slow combustion of aluminium trimethyl

1965 ◽  
Vol 288 (1412) ◽  
pp. 123-132 ◽  
Keyword(s):  
Free Radical ◽  
Organic Compounds ◽  
Initial Rate ◽  
Inert Gases ◽  
Spontaneous Ignition ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Ambient Temperatures ◽  
Slow Combustion ◽  
Rate Of Reaction

Kinetic and analytical studies of the gaseous oxidation of aluminium trimethyl at ambient temperatures and at pressures well below those required for spontaneous ignition have shown that, in contrast to the oxidations of less electron-deficient metal alkyls, no peroxides can be detected and no volatile oxygenated organic compounds are formed. Methane, traces of hydrogen and a solid methoxymethyl compound of aluminium are the only products. The initial rate of reaction is approximately proportional to the first power of the alkyl pressure and to the square of the oxygen pressure; it is little influenced by temperature or by inert gases but is lowered by an increase in surface. The observed kinetic and analytical results can be accounted for in terms of a free radical chain mechanism in which termination takes place predominantly at the walls.

Catalysis of hydrogen peroxide dceomposition by 2-electron oxidation and reduction

1959 ◽  
Vol 12 (2) ◽  
pp. 147 ◽  
Author(s):  
NK King ◽  
ME Winfield
Keyword(s):  
Hydrogen Peroxide ◽  
Free Radical ◽  
Radical Formation ◽  
Single Electron ◽  
Chain Mechanism ◽  
Radical Chain ◽  
Radical Chain Mechanism ◽  
Free Radical Formation ◽  
Decomposition Of H2o2

A thermodynamical argument is used to support the suggestion made elsewhere that the more common radical chain mechanism for catalysed decomposition of H2O2 need not predominate if the catalyst can readily undergo a reversible 2-electron oxidation. How complete the exclusion of free radical formation may be depends upon the redox characteristics of the catalyst and on whether its oxidation by two single-electron steps is readily reversible along the same path.

ChemInform Abstract: Free-Radical Functionalization of β-Amino Alcohols via 1,5-Hydrogen Atom Abstraction in 1,3-Oxazolidines.

ChemInform ◽  
2010 ◽  
Vol 30 (50) ◽  
pp. no-no
Author(s):  
Rajendra Gosain ◽  
Andrew M. Norrish ◽  
Mark E. Wood
Keyword(s):  
Free Radical ◽  
Hydrogen Atom ◽  
Amino Alcohols ◽  
Hydrogen Atom Abstraction ◽  
Radical Functionalization
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