Réarrangement thermique de N-acyl-2,2-diméthylaziridines substituées : Une étude mécanistique

Besbes, Néji; Ayed, Tahra; Pale, Patrick; Tangour, Bahoueddine

doi:10.1016/j.crci.2008.07.002

Cited by 5 publications

(4 citation statements)

References 26 publications

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“…23 The structures of these products 1-4 were already confirmed by IR, 1 H NMR and 13 C NMR and also by comparing its authentic samples. 19 Similarly, we followed the evolution of product formation based on the X% H 2 SO 4 by wt. in water.…”

Section: Resultsmentioning

confidence: 99%

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Experimental and theoretical rearrangement of N-acyl-2,2- dimethylaziridines in acidic medium

et al. 2016

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The acid isomerization of N-acyl-2,2-dimethylaziridines 1 in concentrated sulfuric acid at room temperature leads to oxazolines 2 but the neutral hydrolysis of 1 in pure water at room temperature leads to amidoalcohols 3. However, the use of aqueous solutions of H 2 SO 4 at different concentrations at room temperature leads to a mixture of oxazolines 2, amidoalcohols 3 and allylamides 4 with yields depending on the acidity of the medium and the nature of the acyl group. A mechanism has been suggested to explain the formation of these three products. DFT calculations employing the Gaussian 09 program with DFT/B3LYP methods and 6-311++G(2d,2p) basis set were carried out which gave the most stable geometry as well as their atomic charge distributions of compounds 1-4.

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Section: Resultsmentioning

confidence: 99%

“…2.2a Synthesis of N-acylaziridines: N-acyl-2,2-dimethylaziridines 1a-e were prepared from 2,2dimethylaziridine and various acyl chorides with an excess of triethylamine in dry benzene according to known procedures. 19 2.2b Typical procedure of the rearrangement of Nacylaziridines 1:…”

Section: Synthesismentioning

confidence: 99%

Experimental and theoretical rearrangement of N-acyl-2,2- dimethylaziridines in acidic medium

et al. 2016

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“…Le re ´arrangement des aziridines 1 en compose ´s 2-4 a `la tempe ´rature ambiante est un re ´sultat surprenant. En effet, nous avons obtenu les me ´thallylamides 2 par chauffage de 1 dans le tolue `ne a `reflux pendant deux jours [7]. Les oxazolines 3 sont pre ´pare ´es par action de l'acide sulfurique concentre ´sur les aziridines 1a-d pendant deux heures a `la tempe ´rature ambiante [8].…”

Section: Re ´Sultats Et Discussionunclassified

“…La quantite ´d'eau physisorbe ´e existantes dans ces supports est de ´termine ´e par chauffage dans une e ´tuve de type Memmert pendant deux heures a `150 8C. (7,8), 292 (39,2 ; M. + ), 290 (20,3), 277 (22,3), 215 (10,5), 200 (6,3), 171 (16,3), 149 (4,3), 135 (5,3), 134 (8,5), 131 (8,1), 117 (8,4), 116 (6,2), 106 (8,6), 105 (100), 91 (10,0), 78 (7,1), 77 (57,2), 69,9 (6,7), 55 (8,4), 50,9 (10,9), 40,9 (5,0), 39 (4,7), 28 (9,5).…”

Section: De´termination Des Caracte´ristiques Physiques Des Supportsunclassified

Transformations de N-acylaziridines catalysées par des supports à base de silice et d’alumine : une élucidation mécanistique

Besbes

Jellali

Pale

et al. 2010

Comptes Rendus. Chimie

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Theoretical investigations on the mechanistic pathway of the thermal rearrangement of substituted N-acyl-2,2-dimethylaziridines

Arfaoui

Besbes

2013

J Mol Model

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The mechanism of the thermal rearrangement of substituted N-acyl-2,2-dimethylaziridines 1 has been studied using quantum chemistry methods. Geometries of reactants, transition states and products have been optimized at the B3LYP/6-311++G(2d,2p) level. Relative energies for various stationary points have been determined and reaction identified by IRC calculations. The results show that thermal rearrangements occur in three ways. Firstly, the transition state TS 1 in which a hydrogen atom of methyl groups migrates from primary carbon to oxygen of amid group to give the N-methallylamide 2. The second is via the transition state TS 2 in which the attack of oxygen to the tertiary carbon yields the oxazoline 3. The third is via the transition state TS 3 in which a hydrogen migrate from the secondary carbon to oxygen to give the vinylamide 4. In order to get insights into the factors determining the exact nature of its interactions with electrophiles, the application of reactivity parameters derived from density functional theory in a local sense, in particular the softness and Fukui function, to interpret and predict the mechanisms of the thermal decomposition of the N-acyl-2,2-dimethylaziridines 1, has been discussed.

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Réarrangement thermique de N-acyl-2,2-diméthylaziridines substituées : Une étude mécanistique

Abstract: b Unite ´de recherche chimie the ´orique et re ´activite ´, institut pre ´paratoire aux e ´tudes d'inge ´nieurs d'El Manar,

Cited by 5 publications

References 26 publications

Experimental and theoretical rearrangement of N-acyl-2,2- dimethylaziridines in acidic medium

Experimental and theoretical rearrangement of N-acyl-2,2- dimethylaziridines in acidic medium

Transformations de N-acylaziridines catalysées par des supports à base de silice et d’alumine : une élucidation mécanistique

Theoretical investigations on the mechanistic pathway of the thermal rearrangement of substituted N-acyl-2,2-dimethylaziridines

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