Amination of Nitroazaaromatics.

Woźniak, M.; Plas, H. C. Van Der; Vada, S.; Rossberg, Harald; Schulz, B.; Chanon, Michel; Striley, Cindy; Weidlein, Johann; Nasiri, Ahmad; Okada, Yoshito

doi:10.3891/acta.chem.scand.47-0095

Cited by 22 publications

(7 citation statements)

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“…Recently, there has been growing interest in the direct nucleophilic replacement of hydrogen with the amino group in electrophilic arenes . The Chichibabin reaction, replacement of hydride anion in the reaction of electrophilic heterocycles with sodium or potassium amides, was recently substantially improved and extended by use of an external oxidant, KMnO 4 in liquid ammonia . This oxidative variant of the Chichibabin reaction is also applicable to some electrophilic nitroarenes.…”

Section: Introductionmentioning

confidence: 99%

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Mąkosza

Bialecki

1998

J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Mąkosza

Bialecki

1998

J. Org. Chem.

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Section: Amination Reactionsmentioning

confidence: 99%

“…We have obtained the 2,5-substitution pattern by the use the oxidative amination reaction (ONSH) [16] and the Vicarious Nucleophilic Substitution (VNS) method [17]. The oxidative amination of aromatic and heteroaromatic compounds is an important reaction for the amination of activated substrates [16]. It is reported that the reaction of 3-nitropyridine in liquid ammonia and KMnO 4 gave a mixture of 2-amino-5-nitropyridine (14a, relative amount 1), 2-amino-3-nitropyridine (14b, relative amount 1.7) and 4-amino-3-nitropyridine (14c, relative amount 1.3) [18].…”

Section: Amination Reactionsmentioning

confidence: 99%

Nitropyridines, their synthesis and reactions

Bakke

2005

Journal of Heterocyclic Chemistry

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Reaction of pyridine and substituted pyridines with N2O5 in an organic solvent gives the N‐nitropyridinium ion. When this is reacted with SO2/HSO3‐ in water, 3‐nitropyridine is obtained (77 % yield). With substituted pyridines the method gives good yields for 4‐substituted and moderate yields for 3‐substituted pyridines. The reaction mechanism is not an electrophilic aromatic substitution but one in which the nitro group migrates from the 1‐position to the 3‐position by a [1,5] sigmatropic shift. From 3‐nitropyridine, 5‐nitropyridine‐2‐sulfonic acid is formed in a two step reaction. From this, a series of 2‐substituted‐5‐nitropyridines has been synthesized. 3‐Nitropyridine and 4‐substituted‐3‐nitropyridines have been substituted with ammonia and amines by the vicarious nucleophilic substitution (VNS) method with ammonia and amines and by the oxidative substitution method in the position para to the nitro group. High regioselectivities and yields have been obtained in both cases to afford a series of 4‐substituted‐2‐alkylamino‐5‐nitropyridines. The VNS method has also been used in alkylation reactions with 3‐nitropyridines to form dichloromethyl‐and alkoxycarbomethyl‐β‐nitropyridines. From the appropriate substituted nitropyridines imidazopyridines and azaindoles have been formed.

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“…We have also obtained the 2,5-substitution pattern by the use of vicarious nucleophilic substitution (VNS) [25] and the oxidative amination reaction (ONSH) [26].…”

Section: Substitution Reactionsmentioning

confidence: 99%

“…As hydroxylamine is more available then the aminotriazole, it may be the reagent of choice especially for large-scale preparations. The oxidative amination of aromatic and heteroaromatic compounds is an important reaction for the amination of activated substrates [26]. It is reported that the reaction of 3-nitropyridine in liquid ammonia and KMnO 4 gave a mixture of 2-amino-5-nitropyridine (20a, relative amount 1), 2-amino-3-nitropyridine (20b, relative amount 1.7), and 4-amino-3-nitropyridine (20c, relative amount 1.3) [28].…”

Section: Scheme 9 Scheme 10mentioning

confidence: 99%

Nitropyridines: Synthesis and Reactions

Bakke

2004

ChemInform

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Reaction of pyridine and substituted pyridines with N 2 O 5 in an organic solvent gives the N-nitropyridinium ion. When this is reacted with SO 2 /HSO 3 -in water, 3-nitropyridine is obtained (77 % yield). With substituted pyridines, the method gives good yields for 4-substituted and moderate yields for 3-substituted pyridines. The reaction mechanism is not an electrophilic aromatic substitution, but one in which the nitro group migrates from the 1-position to the 3-position by a [1,5] sigmatropic shift. From 4-aminopyridine, imidazo[4,5-c]pyridines have been synthesized. From 3-nitropyridine, 5-nitropyridine-2-sulfonic acid is formed in a two-step reaction. From this, a series of 2-substituted-5-nitropyridines has been synthesized. 3-Nitropyridine and 4-substituted-3-nitropyridines have been substituted with ammonia and amines by the vicarious substitution method and by the oxidative substitution method in the position para to the nitro group. High regioselectivities and yields have been obtained in both cases to afford a series of 4-substituted-2-alkylamino-5-nitropyridines.

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Amination of Nitroazaaromatics.

Cited by 22 publications

References 0 publications

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Nitropyridines, their synthesis and reactions

Nitropyridines: Synthesis and Reactions

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