Simple Synthesis of Dimethyl Nitrobenzhydrylphosphonates and Heteroarylnitroarylacetonitriles via Vicarious Nucleophilic Substitution (VNS) Reaction

Synthesis ◽  
2020 ◽  
Vol 53 (01) ◽  
pp. 175-181
Author(s):  
Mieczysław Mąkosza ◽  
Małgorzata Bechcicka ◽  
Krzysztof Wojciechowski

Acetals of dimethyl phenyl- and heteroaryl-α-hydroxymethanephosphonates were deprotonated to generate carbanions, which enter the vicarious nucleophilic substitution (VNS) of hydrogen in aromatic nitro compounds to form 4-nitrobenzhydrylphosphonates and α-heteroaryl-4-nitrobenzylphosphonates. Similarly acetals of cyano­hydrins of heteroaromatic aldehydes (furfural and 2-formylthiophene) react to form heteroaryl 4-nitroarylacetonitriles. The anion of the hemiacetal of acetaldehyde is an efficient leaving group in the base-induced β-elimination step – the crucial step in the VNS reaction. The reaction selectively occurred at the para-position to the nitro group.

2008 ◽  
Vol 86 (7) ◽  
pp. 682-685 ◽  
Author(s):  
Barbara Szpakiewicz ◽  
Maria Grzegożek

3-, 5-, 6-, 7- and 8-Nitroquinolines react with 4-amino-1,2,4-triazole in basic medium (potassium tert-butoxide-dimethyl sulfoxide) giving amino products of the vicarious nucleophilic substitution (VNS) of hydrogen, predominantly at ortho position to the nitro group, except 8-nitroquinoline, which reacts at para position. Additionally, furazano[3,4-f]- and furazano[3,4-h]quinoline were obtained in the case of 5- and 8- nitroquinoline, respectively. 2-Nitroquinoline was aminated to 2-quinolino(1,2,4-triazol-4-yl)amine in these conditions.Key words: nitroquinolines, vicarious nucleophilic substitution (VNS), 4-amino-1,2,4-triazole.


ChemInform ◽  
2016 ◽  
Vol 47 (3) ◽  
Author(s):  
Maria Luisa Di Gioia ◽  
Antonella Leggio ◽  
Isabella Federica Guarino ◽  
Vanessa Leotta ◽  
Emanuela Romio ◽  
...  

1967 ◽  
Vol 20 (11) ◽  
pp. 2381 ◽  
Author(s):  
ID Rae

The differences between proton mangetic resonance spectra of aromatic nitro compounds in deuterochloroform and dimethyl sulphoxide solutions are interpreted in terms of increased steric requirements of the nitro group in the latter solvent. In suitably ortho-substituted aromatic nitro compounds this leads to twisting of the nitro group about the Ar- N bond.


1964 ◽  
pp. 441-447
Author(s):  
E.YU. ORLOVA ◽  
G.M. SHUTOV ◽  
V.L. ZBARSKII ◽  
V.F. ZHILIN

2015 ◽  
Vol 56 (39) ◽  
pp. 5341-5344 ◽  
Author(s):  
Maria Luisa Di Gioia ◽  
Antonella Leggio ◽  
Isabella Federica Guarino ◽  
Vanessa Leotta ◽  
Emanuela Romio ◽  
...  

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