scholarly journals Diazomethane umpolung atop anthracene: an electrophilic methylene transfer reagent

2018 ◽  
Vol 9 (6) ◽  
pp. 1540-1543 ◽  
Author(s):  
Maximilian Joost ◽  
Wesley J. Transue ◽  
Christopher C. Cummins
Keyword(s):  
Nitrogen Atom ◽  
Terminal Nitrogen Atom

Formal addition of diazomethane's terminal nitrogen atom to the 9,10-positions of anthracene yields H2CN2A (1, A = C14H10 or anthracene).

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 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.

Nitrogen Atom Densities in Rare Gas Diluted N2 Plasmas with Capacitive and Inductive Coupling

2008 ◽  
Vol 128 (10) ◽  
pp. 615-618 ◽  
Author(s):  
Takeshi Kitajima ◽  
Akihiro Kubota ◽  
Toshiki Nakano
Keyword(s):  
Nitrogen Atom ◽  
Inductive Coupling ◽  
Rare Gas

Configuration on the C=N double bond of monosubstituted amidines and amidoximes

1989 ◽  
Vol 54 (12) ◽  
pp. 3245-3252 ◽  
Author(s):  
Bernard Tinant ◽  
Janine Dupont-Fenfau ◽  
Jean-Paul Declercq ◽  
Jaroslav Podlaha ◽  
Otto Exner
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Steric Effects ◽  
Model Compounds ◽  
X Ray ◽  
Analogous Model

Configuration on the C=N double bond of amidines and amidoximes is controlled by steric effects on the second nitrogen atom but there is a difference in the case of N’-monosubstituted derivatives: amidines prefer E configuration (conformation around the C-N bond sp) and amidoximes Z configuration (conformation ap). This was confirmed by the X-ray structures of two analogous model compounds N,N’-dimethyl-4-nitrobenzamidine (monoclinic, P21c, a = 10.855(3), b = 11.043(3), c = 8.593(3) Å, β = 105.69(2)°, V = 991.8(5) Å3, Z = 4, Dx = 1.29 g cm-3, CuKα, λ = 1.5418 Å, μ = 7.91 cm-1, F(000) = 408, T = 291 K, R = 0.065 for 1 265 observed reflections) and N’-methyl-4-nitrobenzamidoxime (monoclinic, P21/a, a = 6.699(2), b = 24.178(9), c = 6.075(2) Å, β = 106.20(3)°, V = 944.9(6) Å3, Z = 4, Dx = 1.37 g cm-3, CuKα, λ = 1.5418 Å, μ =9.22 cm-1, F(000) = 408, T = 291 K, R = 0.079 for 1 278 observed reflections).

Dirhodium-Catalyzed Chemo- and Site-Selective C–H Amidation of N,N-Dialkylanilines

Synlett ◽  
2020 ◽  
Author(s):  
Yoshihiro Ueda ◽  
Gong Chen ◽  
Kenta Arai ◽  
Kazuhiro Morisaki ◽  
Takeo Kawabata
Keyword(s):  
Nitrogen Atom ◽  
Aromatic Ring ◽  
Methyl Group ◽  
Site Selective

AbstractA method for dirhodium-catalyzed C(sp3)–H amidation of N,N-dimethylanilines was developed. Chemoselective C(sp3)–H amidation of N-methyl group proceeded exclusively in the presence of C(sp2)–H bonds of the electron-rich aromatic ring. Site-selective C(sp3)–H amidation proceeded exclusively at the N-methyl group of N-methyl-N-alkylaniline derivatives with secondary, tertiary, and benzylic C(sp3)–H bonds α to a nitrogen atom.

A new strategy for the construction of polycycles bearing a nitrogen atom on the ring fusion

2002 ◽  
Vol 43 (28) ◽  
pp. 4963-4968 ◽  
Author(s):  
Reynald Deléens ◽  
Arnaud Gautier ◽  
Serge R Piettre
Keyword(s):  
Nitrogen Atom ◽  
Ring Fusion ◽  
New Strategy

Regiospezifische Insertion von [SCN]- und [SeCN]- in die S – C- bzw. Se– C-Bindung Übergangsmetall-koordinierter Thietane und SelenetaneRegiospecific Insertion of [SCN]- and [SeCN]- in the S–C- and Se–C-Bond of Transition-Metal-Coordinated Thietanes and Selenetanes

1993 ◽  
Vol 48 (11) ◽  
pp. 1613-1620 ◽  
Author(s):  
Helmut Fischer ◽  
Claudia Kalbas ◽  
Carsten Troll ◽  
Klaus H. Fluck
Keyword(s):  
Nitrogen Atom ◽  
Transition Metal ◽  
Structure Analysis ◽  
Trans Isomer ◽  
X Ray ◽  
Tungsten Complexes ◽  
Membered Heterocycle

Pentacarbonyl(thietane)tungsten complexes react with thiocyanate, [SCN]-, and SiO2/H2O by insertion of the CN group into a S—C bond of the four-membered heterocycle, 1,3-migration of the pentacarbonyltungsten fragment and protonation of the nitrogen atom to give tungsten-coordinated thiazinthione complexes. Analogously, the reactions of a thietane tungsten complex with [SeCN]- and SiO2/H2O affords a thiazinselone complex. A selenazinthione complex is obtained from a selenetane complex and [SCN]- (+ SiO2/H2O). The insertions are regiospecific and stereoselective. The structure of the trans-isomer of a pentacarbonyl-(thiazinthione) complex has been established by X-ray structure analysis.

Chemistry of bicyclic 5-6 systems: Synthesis of oxazolo[3,2-a]pyridines and their salts with a ring-junction nitrogen atom

2019 ◽  
Vol 49 (20) ◽  
pp. 2591-2629 ◽  
Author(s):  
Mohamed Monier ◽  
Ahmed El-Mekabaty ◽  
Doaa Abdel-Latif ◽  
Khaled M. Elattar
Keyword(s):  
Nitrogen Atom ◽  
Ring Junction
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