An original method for the synthesis of quinazolines

Аксенов, А. В.; Lyakhovnenko, A. S.; Kugutov, M. M.

doi:10.1007/s10593-010-0480-7

Cited by 6 publications

(2 citation statements)

References 3 publications

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“…1,3,5-Triazine (4a) is added to the reaction mixture obtained from anisole 1b or phenol 1c and heated for 4 h at 90-100°C to give quinolines 5a,b* in 54% and 49% yield respectively. _______ * Reported in our preliminary communication [4]. The reaction proceeds similarly if naphthalene 1a is used as the starting compound.…”

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confidence: 94%

New method for the direct electrophilic amination of aromatic compounds and its use in the annelation of the pyrimidine ring

Аксенов

Lyakhovnenko

Kugutov

2011

Chem Heterocycl Comp

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A method has been developed for the synthesis of aromatic amines by the amination of the corresponding aromatic compounds using sodium azide in PPA. A method for the synthesis of quinazolines and benzo [h]quinazolines using this reaction and the subsequent reaction of the intermediates with 1,3,5-triazines has been developed.In previous work [1, 2], we discovered a new reagent system for the electrophilic amination of aromatic compounds and shown its applicability for perimidines. In the present work, we have extended this method for the synthesis of other aromatic amines and shown its applicability in combination with 1,3,5-triazines for the annelation of the pyrimidine ring to aromatic compounds.As noted in our previous work [1, 2], the reaction of perimidines with a threefold excess of PPA at 80-90°C leads to the corresponding 6(7)-aminoperimidines in high yield. The PPA sample used containing 86% P 2 O 5 was obtained according to Uhlig [3].We might have assumed that this reagent system would be applicable for the amination of other aromatic compounds. Indeed, we showed that the reaction proceeds analogously with naphthalene to give 1-naphthylamine (2a) in 31% yield. The low yield is mostly a consequence of sublimation of naphthalene from the reaction mixture. NH 2 2) H 2 O 1a 2a 1) NaN 3 /PPA

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confidence: 94%

New method for the direct electrophilic amination of aromatic compounds and its use in the annelation of the pyrimidine ring

Аксенов

Lyakhovnenko

Kugutov

2011

Chem Heterocycl Comp

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“…Considering an extremely high practical importance of aromatic amines, numerous attempts have been done to directly introduce amino group into aromatics via one‐step route. For that purpose such nitrogen‐containing compounds as ammonia,, hydroxylamine, its salts and derivatives, and hydrazoic acid were used. However, ammonia and hydroxylamines showed low aminating ability.…”

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confidence: 99%

Mechanism of Direct Electrophilic Aromatic Amination: an Electrophile is Found by Quantum‐Chemical Study

et al. 2019

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Direct amination is an extremely valuable reaction, allowing for the one-step preparation of aromatic amines. However, its mechanism was poorly studied. Here, for the first time, using quantum chemical calculations, we have shown that direct amination of arenes by hydrazoic acid follows the classical S E Ar mechanism with aminodiazonium cation H 2 N 3 + as electrophile. The peculiarity of H 2 N 3 + electronic structure has been described using our novel method for tracing the molecular orbitals. The located stationary points and transition states allowed us to define direct amination as S E Ar reaction, which rate is determined by early transition state between πand σcomplexes. Considering the calculated reaction constant 1 and an early transition state, we placed direct amination of arenes by HN 3 somewhere in-between nitration and halogenations. Our results explain the accumulated experimental data and open a prospect for the development of the new aminating agents working in milder conditions.[a] K.

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