Reactions of aryl diazonium salts and alkyl arylazo ethers. XI. Further evidence for the mechanism of dediazoniation in basic alcoholic solution

1983 ◽  
Vol 36 (5) ◽  
pp. 1031 ◽  
Author(s):  
TJ Broxton ◽  
MJ Mcleish
Keyword(s):  
Free Radical ◽  
Nitrogen Atom ◽  
Solvent Effect ◽  
Alcoholic Solution ◽  
Diazonium Salts ◽  
Hydride Abstraction ◽  
Terminal Nitrogen Atom ◽  
Methoxide Ion ◽  
Diazonium Ion

A comparison of the relative amounts of dediazoniation, SNAr and aryne reactions of 4-chloro-3- nitrobenzenediazonium ion with methoxide ion in CH3OH and in CD3OH confirms that the dediazoniation reaction involves hydride abstraction from the alkoxide ion by the electrophilic terminal nitrogen atom of the diazonium ion. Furthermore, the relative amounts of anionic and free-radical dediazoniation are the same in CH3OH and in CD3OH. This confirms that the partitioning between the free-radical and anionic pathways for dediazoniation is on the aryl diimide and not on the free diazonium ion. Some previously reported results on the solvent effect (methanol against ethanol) for the reaction have been reinterpreted in the light of the above conclusions.

scholarly journals Solvent Effect on the Free Radical Phenylation with Phenylazotriphenylmethane

1973 ◽  
Vol 46 (2) ◽  
pp. 546-550 ◽  
Author(s):  
Michio Kobayashi ◽  
Hiroshi Minato ◽  
Nobuko Watanabe
Keyword(s):  
Free Radical ◽  
Solvent Effect ◽  
Radical Phenylation

scholarly journals Kinetics of Free Radical Polymerization of N-Substituted Amides and Their Structural Implications

2016 ◽  
Vol 2016 ◽  
pp. 1-9 ◽  
Author(s):  
Anca Aldea ◽  
Ana-Maria Albu ◽  
Alina Nicolescu ◽  
Victorita Tecuceanu
Keyword(s):  
Hydrogen Bonding ◽  
Free Radical ◽  
Nitrogen Atom ◽  
Steric Hindrance ◽  
Solvent Polarity ◽  
Hydrogen Bonding Interaction ◽  
H Nmr ◽  
Bonding Interaction ◽  
Kinetics Of ◽  
C Nmr

Two N-substituted amides (N-acryloyl morpholine and N-methyl-N-vinylacetamide) were polymerized in different solvents using radical initiator. The tacticity of obtained polymers was determined by 400 MHz1H-NMR and13C-NMR. At a given temperature, the syndiotacticity increased with increasing the solvent polarity. This solvent effect may be related to the hydrogen bonding interaction among solvent, monomer, and/or growing species. A peculiar aspect regards the steric hindrance at the nitrogen atom.

NMR and DFT investigations of the substituent and solvent effect on amino-imino tautomerism in acridin-9-amines substituted at the exocyclic nitrogen atom

2005 ◽  
Vol 18 (8) ◽  
pp. 870-879 ◽  
Author(s):  
Youssif Ebead ◽  
Agnieszka Wróblewska ◽  
Karol Krzymiński ◽  
Janusz Rak ◽  
Jerzy Błażejowski
Keyword(s):  
Nitrogen Atom ◽  
Solvent Effect ◽  
Exocyclic Nitrogen Atom

Free-radical diazocoupling. A new general reaction of diazonium salts

1982 ◽  
Vol 47 (9) ◽  
pp. 1759-1761 ◽  
Author(s):  
Attilio Citterio ◽  
Francesco Minisci
Keyword(s):  
Free Radical ◽  
Diazonium Salts ◽  
General Reaction

Diazonium salt-based photoiniferter as a new efficient pathway to clay–polymer nanocomposites

RSC Advances ◽  
2016 ◽  
Vol 6 (91) ◽  
pp. 88126-88134 ◽  
Author(s):  
Hanène Salmi-Mani ◽  
Zouhair Ait-Touchente ◽  
Aazdine Lamouri ◽  
Benjamin Carbonnier ◽  
Jean-François Caron ◽  
...  
Keyword(s):  
Free Radical ◽  
Polymer Nanocomposites ◽  
Glycidyl Methacrylate ◽  
Diazonium Salt ◽  
Diazonium Salts ◽  
Mass Loading ◽  
Organic Mass ◽  
Free Radical Photopolymerization

Diazonium salts were used to prepare clay–polymer nanocomposites by living free radical photopolymerization of glycidyl methacrylate. The resulting intercalated nanocomposites have an organic mass loading of ∼41 wt% and a polymer-rich surface.

ChemInform Abstract: Polar Effects in Reactions of Carbon-Centered Radicals with Diazonium Salts: Free-Radical Diazocoupling.

ChemInform ◽  
1992 ◽  
Vol 23 (51) ◽  
pp. no-no
Author(s):  
F. MINISCI ◽  
F. COPPA ◽  
F. FONTANA ◽  
G. PIANESE ◽  
L. ZHAO
Keyword(s):  
Free Radical ◽  
Diazonium Salts

scholarly journals Theoretical Studies on the Mechanism of the Azido-Tetrazole of Azido-s-triazine

2015 ◽  
Vol 10 (2) ◽  
pp. 1934578X1501000
Author(s):  
Xiao-Qin Liang ◽  
Jin-Jun Zhou ◽  
Yan Zheng ◽  
Feng Ma
Keyword(s):  
Nitrogen Atom ◽  
Electronic Structures ◽  
Bond Angle ◽  
Nbo Analysis ◽  
Molecular Structures ◽  
Azido Group ◽  
Free Energy Barrier ◽  
Azide Group ◽  
Cyclization Process ◽  
Terminal Nitrogen Atom

The B3LYP/aug-cc-pvDZ level of theory has been applied to the study of the molecular structures, electronic structures and the azido-tetrazole isomerization of 1-azido-s-triazine, 1,3-diazido-s-triazine and 1,3,5-triazido-s-triazine. NBO analysis was applied to investigate the atomic natural charge and stabilization interaction energies among molecules. The results showed that the reaction initially proceeds through the loss of the linearity of the azido group and the approaching of the terminal nitrogen atom of the azide group to the nitrogen atom of the ring. This is followed by an attack of the lone pairs on N atoms in the ring to the azido group, leading to the formation of the N-N bonds. Many factors, including bending of the bond angle, electrostatic attraction, orbital delocalization and the stabilization interaction give rise to a large free energy barrier for the cyclization process. The results also show that the second and third cyclization is relatively easier than the first one.

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