Reactions of aromatic radical anions. III. Evidence for an alkyl radical-radical anion combination mechanism for alkylation of sodium naphthalenide with alkyl halides

1968 ◽  
Vol 90 (25) ◽  
pp. 7160-7162 ◽  
Author(s):  
G. Dann. Sargent ◽  
Glenn A. Lux
Keyword(s):  
Alkyl Radical ◽  
Radical Anion ◽  
Alkyl Halides ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Sodium Naphthalenide

Fragmentation Rates of Aromatic Radical Anions and the π*— σ* Orbital Crossing Point

1984 ◽  
Vol 39 (1) ◽  
pp. 49-54 ◽  
Author(s):  
H. O. Villar ◽  
E. A. Castro ◽  
R. A. Rossi
Keyword(s):  
Carbon Atom ◽  
Molecular Orbital ◽  
Qualitative Agreement ◽  
Radical Anion ◽  
Reaction Coordinate ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Orbital Crossing ◽  
Crossing Point

The reaction coordinate of the fragmentation of aromatic radical anions with nucleofugal groups was studied by the INDO and MNDO techniques. The reaction coordinate turned out as the stretching between the nucleofugal group bonded to the carbon atom of the aryl moiety. It was found that to fragment a π* radical anion, the odd electron has to be transferred to the σ* molecular orbital of the aryl-nucleofugal bond by an orbital crossing, which is reached by the lengthening of this bond. There is a qualitative agreement between the length of the bond to reach the orbital crossing point and the experimental fragmentation rates of the aromatic radical anions. Finally, some considerations about the σ-π coupling are made, since it is defining the possibility of a transfer from the π* to the σ* molecular orbital.

Metal Chloride Reductions with Aromatic Radical Anions. The Magnesium Chloride Catalysed Cleavage of Tetrahydrofuran by Sodium Naphthalene Radical Anion

2007 ◽  
Vol 72 (5-6) ◽  
pp. 589-598
Author(s):  
Barry R. Steele ◽  
Georgios A. Heropoulos ◽  
Constantinos G. Screttas
Keyword(s):  
Alkali Metal ◽  
Organic Synthesis ◽  
Magnesium Chloride ◽  
Radical Anion ◽  
Catalytic Amount ◽  
Metal Chloride ◽  
Metal Salts ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Metallic Magnesium

Activated metals for organic synthesis are often prepared by reduction of metal salts using alkali metal aromatic radical anions. The reduction of magnesium chloride has been examined by NMR. Whereas the expected reduction to the metal occurred with lithium or potassium naphthalene radical anion, under certain conditions, with sodium naphthalene radical anion, no metallic magnesium was precipitated and dark red solutions were obtained. It was also found that solutions of sodium naphthalene radical anion in tetrahydrofuran, in the presence of a catalytic amount of magnesium chloride, quickly became diamagnetic. A mechanism involving bimetallic species is postulated to explain the results.

scholarly journals Competitive Electron Transfer and SN2 Reactions of Aromatic Radical Anions with Alkyl Halides and Methanesulfonates.

1998 ◽  
Vol 52 ◽  
pp. 51-61 ◽  
Author(s):  
Heidi Skovbak Sørensen ◽  
Kim Daasbjerg ◽  
Lennart Eberson ◽  
Björn Åkermark ◽  
John H. Wagenknecht ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Alkyl Halides ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Sn2 Reactions

Reactions of aromatic radical anions. X. Syntheses using a conveniently recoverable radical anion precursor

1973 ◽  
Vol 14 (23) ◽  
pp. 2097-2100 ◽  
Author(s):  
Shelton Bank ◽  
Matthew Platz
Keyword(s):  
Radical Anion ◽  
Radical Anions ◽  
Aromatic Radical

On the Dissociation of Aromatic Radical Anions in Solution. 1. Formulation and Application top-Cyanochlorobenzene Radical Anion

2003 ◽  
Vol 107 (51) ◽  
pp. 11271-11291 ◽  
Author(s):  
Damien Laage ◽  
Irene Burghardt ◽  
Thomas Sommerfeld ◽  
James T. Hynes
Keyword(s):  
Radical Anion ◽  
Radical Anions ◽  
Aromatic Radical

Stability of radical anions derived from substituted 5-nitrofurans investigated by ESR spectroscopy

1985 ◽  
Vol 50 (7) ◽  
pp. 1594-1601 ◽  
Author(s):  
Jiří Klíma ◽  
Larisa Baumane ◽  
Janis Stradinš ◽  
Jiří Volke ◽  
Romualds Gavars
Keyword(s):  
Radical Anion ◽  
High Stability ◽  
Esr Spectroscopy ◽  
Reaction Path ◽  
Order Reaction ◽  
Second Order ◽  
Radical Anions ◽  
Second Order Reaction ◽  
Unpaired Electron Density ◽  
The Stability

It has been found that the decay in dimethylformamide and dimethylformamide-water mixtures of radical anions in five of the investigated 5-nitrofurans is governed by a second-order reaction. Only the decay of the radical anion generated from 5-nitro-2-furfural III may be described by an equation including parallel first- and second-order reactions; this behaviour is evidently caused by the relatively high stability of the corresponding dianion, this being an intermediate in the reaction path. The presence of a larger conjugated system in the substituent in position 2 results in a decrease of the unpaired electron density in the nitro group and, consequently, an increase in the stability of the corresponding radical anions.

Electron affinities of benzaldehydes. Substituent effects on stabilities of aromatic radical anions

1993 ◽  
Vol 34 (26) ◽  
pp. 4223-4226 ◽  
Author(s):  
Masaaki Mishima ◽  
Chul Huh ◽  
Hirotaka Nakamura ◽  
Mizue Fujio ◽  
Yuho Tsuno
Keyword(s):  
Substituent Effects ◽  
Radical Anions ◽  
Electron Affinities ◽  
Aromatic Radical

Specific Effects of Room Temperature Ionic Liquids on Cleavage Reactivity:  Example of the Carbon−Halogen Bond Breaking in Aromatic Radical Anions

2004 ◽  
Vol 108 (29) ◽  
pp. 6175-6182 ◽  
Author(s):  
Corinne Lagrost ◽  
Said Gmouh ◽  
Michel Vaultier ◽  
Philippe Hapiot
Keyword(s):  
Ionic Liquids ◽  
Room Temperature ◽  
Halogen Bond ◽  
Room Temperature Ionic Liquids ◽  
Bond Breaking ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Specific Effects
Sign in / Sign up

Export Citation Format

Share Document