.sigma.-Adduct formation between azines and liquid ammonia. 47. Frontier orbital interactions in the regioselectivity of the amination of nitroquinolines by liquid ammonia/potassium permanganate

Woźniak, M.; Barański, A.; Nowak, Krystyna

doi:10.1021/jo00235a001

Cited by 29 publications

(5 citation statements)

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“…These changes of the chemical shifts (∆δ = 3.24 −5.22 ppm) are comparable to those reported earlier for the amino σ adducts detected in oxidative dehydroamination of nitroquinolines [4][5][6] . In the case of 5-nitro-(1b) and 8-nitroquinoline (1e) we did not observe NMR signals from the σ adducts linked at the position…”

Section: 02supporting

confidence: 90%

Study of the regioselectivity of vicarious nucleophilic amination of mononitroquinolines with 1,1,1-trimethylhydrazinium iodide (TMHI)

Grzegożek¹,

Szpakiewicz²,

Kowalski³

2009

Arkivoc

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Dedicated to Professor Henk C. van der Plas on the occasion of his 80th anniversary AbstractThe intermediary, covalent σ adducts formed in the reaction of nitroquinolines with the ylide generated from 1,1,1-trimethylhydrazinium iodide (TMHI) were detected by 1 H NMR spectroscopy. Quantum-chemical calculations of the transition state (TS) energy and heats of formation of the σ adducts were done. The results of the calculations agree with high regioselectivity observed for the amination of 3-, 5-, 6-, 7-and 8-nitroquinolines with (TMHI) via a vicarious nucleophilic substitution (VNS) reaction. High yields of the products substituted with amino substituent, mainly in the ortho position relation to the nitro group, are obtained.

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Section: 02supporting

confidence: 90%

Study of the regioselectivity of vicarious nucleophilic amination of mononitroquinolines with 1,1,1-trimethylhydrazinium iodide (TMHI)

Grzegożek¹,

Szpakiewicz²,

Kowalski³

2009

Arkivoc

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“…Thus, treatment of isomeric nitroquinolines 21-24 with potassium methoxide in THF at room temperature produced the corresponding methoxylated nitroquinolines 25-28 in 32-46% isolated yields (Scheme 5). Similarly to the amination of nitroquinolines by potassium permanganate in liquid ammonia, the regioselectivity of the present displacement reaction has been found to obey the LUMO and LUMO ϩ 1 orbital densities 11 and the starting materials were completely consumed under the conditions where the corresponding nitronaphthalene isomers remained almost intact (Table 4).…”

Section: Reaction Of Nitroquinolines 21-24 With Potassium Methoxidementioning

confidence: 53%

Direct methoxylation of nitroarenes and nitroazaarenes with alkaline methoxides via nucleophilic displacement of an aromatic hydrogen atom

Kawakami

Suzuki

2000

J. Chem. Soc., Perkin Trans. 1

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Treatment of 1,3-dinitrobenzene and 5-substituted derivatives with excess potassium or sodium methoxide in 1,3-dimethylimidazolidin-2-one (DMI) at room temperature results in the displacement of an aromatic hydrogen at the 4-position by methoxide, affording 2,4-dinitroanisole and its 6-substituted derivatives, respectively, in low to moderate yield. In contrast, an equimolar reaction under similar conditions leads to the replacement of the nitro group in preference to the ring hydrogen. The reaction does not take place with lithium methoxide as a base. Monoand dinitronaphthalenes and nitroquinolines undergo similar displacement of a hydrogen atom at the position ortho or para to the nitro group, giving the corresponding methoxy derivatives in moderate yield. A slow addition of the nitro compound to a large excess of potassium methoxide under an oxygen atmosphere has been found to enhance the conversion and improve the product yield. On the basis of the product distribution as well as the kinetic isotope effect k H /k D = 2.1, direct displacement of a ring hydrogen atom by methoxide ion has been interpreted in terms of the rate-determining release of an ipso-hydrogen atom as a proton from the initially formed Meisenheimer adduct.

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“…In the initial stage, the hydrazone anion attacks the 5-position of 6-nitroquinoline 6 to form a Meisenheimer intermediate 18. 16,17 This intermediate anion undergoes the nitro-aci-nitro isomerization followed by dehydration to form the anion 19, 18 which then would cyclize via two competing pathways depending on the electronic nature of the ring substituent group of the original chemical aromatic hydrazone.…”

Section: Possible Reaction Mechanismmentioning

confidence: 99%

A straightforward synthesis of some fused aza-arenes via nucleophilic displacement of a ring hydrogen atom in nitroarenes by aromatic hydrazone anions

Uehata

Kawakami

Suzuki

2002

J. Chem. Soc., Perkin Trans. 1

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.sigma.-Adduct formation between azines and liquid ammonia. 47. Frontier orbital interactions in the regioselectivity of the amination of nitroquinolines by liquid ammonia/potassium permanganate

Cited by 29 publications

References 0 publications

Study of the regioselectivity of vicarious nucleophilic amination of mononitroquinolines with 1,1,1-trimethylhydrazinium iodide (TMHI)

Study of the regioselectivity of vicarious nucleophilic amination of mononitroquinolines with 1,1,1-trimethylhydrazinium iodide (TMHI)

Direct methoxylation of nitroarenes and nitroazaarenes with alkaline methoxides via nucleophilic displacement of an aromatic hydrogen atom

A straightforward synthesis of some fused aza-arenes via nucleophilic displacement of a ring hydrogen atom in nitroarenes by aromatic hydrazone anions

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