Thermodynamic and orbital studies of the reactivity of amidine with phosphoryl chloride and thionyl chloride
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Amidines belong to the family of organic superbases; they are generally considered among the strongest useful synthetic auxiliary bases and are widely used in the synthesis of N-heterocycles. In this present work, we have studied the thermodynamic and the orbital recovery of the cyclization reaction of N'-(1H-benzo[d]imidazol-2-yl)-N-cyclopentylacetamidine 1 towards two reagents: the phosphoryl chloride (POCl3) 2 and thionyl chloride (SOCl2) 3. We were particularly interested in studying the different reactivity of the different sites of attack of the N'-(1H-benzo[d]imidazol-2-yl)-N-cyclopentylacetamidine 1, using density functional theory calculations (DFT) with functional B3LYP and standard base 6-311G. We used all the gathered information either from the experimental results obtained for these reactions or from the theoretical study; to exemplify the reactivity of each active site in our amidine 1, among this particular type of reaction under controlled condition to finally elucidate the mechanism of the obtaining of N-heterocycles such as the [1,2a]benzimidazolo-1,3,5,2-triazaphosphorin-2-oxide 6 and the [1,2a]benzimidazolo-1,2,4,6-thiatriazin-1-oxide 7.
KeywordsAmidine DFT Thermodynamic Frontier orbital Phosphoryl chloride Thionyl chloride heterocycle
Authors thank the Tunisian Secretary of State for Scientific Research and Technology for the financial support of this work.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
The work was supported by ministry of high education of Tunisia.
This article does not contain any studies with human participants or animals performed by any of the authors. The manuscript has not been previously published, is not currently submitted for review to any other journal, and will not be submitted elsewhere before a decision is made by this journal.
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