with The Imine and Some of its Derivatives via M06-2X Theory with Basis Set 6-31g(d) and Complete Basis Set

Authors

  • Najwa Hadad Tishreen University

Abstract

The mechanism of  cycloaddition  reactions  of  imine and its derivatives with fluoro ketene were  studied  theoretically  using M06-2X/6-31g(d) level of theory and  complete basis set extrapolation (CBS). It is found that the reaction takes place through a two-step mechanism: i) the first step is the nucleophilic attack of the electronic pair of the nitrogen atom in imine on the central carbon atom of the carbonyl group in ketene forming a zwitterionic (ZW) intermediate, (ii) the second step represents the rate-limiting step of the reaction, during which an attack occurs by a negative charge on the oxygen in the intermediate compound on the carbon atom a of the iminium. The trans-a-lactam and cis-b-lactam isomers are formed along the endo and exo channels, respectively.

The calculated values of Gibbs free energies by the theoretical methods used in this research indicate that the reactions are more spontaneously thermodynamically for R = CH3, while they are faster in the case of R = NH2 kinetically, thus, the activity  of  the  substituted  imines  studied can be arranged thermodynamically and kinetically as follows: and   , respectively,

Author Biography

Najwa Hadad, Tishreen University

Associate Professor, Department of Chemistry, Faculty of Sciences

Downloads

Published

2022-06-16

How to Cite

1.
نجوى حداد. with The Imine and Some of its Derivatives via M06-2X Theory with Basis Set 6-31g(d) and Complete Basis Set. TUJ-BA [Internet]. 2022Jun.16 [cited 2024Nov.24];44(2):45-5. Available from: https://journal.tishreen.edu.sy/index.php/bassnc/article/view/12712

Issue

Vol. 44 No. 2 (2022): Tishreen University Journal of Research and Scientific Studies - Basic Sciences Series

Section

Articles

License

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

The authors retain the copyright and grant the right to publish in the magazine for the first time with the transfer of the commercial right to the Tishreen University Journal -Basic Sciences Series  

 Under a CC BY- NC-SA 04 license that allows others to share the work with of the work's authorship and initial publication in this journal. Authors can use a copy of their articles in their scientific activity, and on their scientific websites, provided that the place of publication is indicted in Tishreen University Journal -Basic Sciences Series .  The Readers have the right to send, print and subscribe to the initial version of the article, and the title of Tishreen University Journal -Basic Sciences Series   Publisher

 

journal uses a CC BY-NC-SA license which mean

You are free to:

  • Adapt — remix, transform, and build upon the material
  •  
  • The licensor cannot revoke these freedoms as long as you follow the license terms.

 

  • Attribution — You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use.
  • NonCommercial — You may not use the material for commercial purposes.
  • ShareAlike — If you remix, transform, or build upon the material, you must distribute your contributions under the same license as the original.
  • No additional restrictions — You may not apply legal terms or technological measures that legally restrict others from doing anything the license permits.