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Can I read Flash Vacuum Pyrolysis (FVP) of cis‐N ‐phenyl‐hexahydro‐2 H ‐benzo[ d ][1,3]oxazin‐2‐imine and Thiazin‐2‐imine Derivatives on EtoBox?

Flash Vacuum Pyrolysis (FVP) of cis‐N ‐phenyl‐hexahydro‐2 H ‐benzo[ d ][1,3]oxazin‐2‐imine and Thiazin‐2‐imine Derivatives by Diana C. Pinilla Peña; Elba N. Ruiz Pereyra; Guadalupe Firpo; Noelia M. Ceballos; Ferenc Fülöp; Zsolt Szakonyi; Ana G. Iriarte; Walter J. Peláez is a Chemistry article available to read on EtoBox.

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## Abstract Cis‐N‐phenyl‐hexahydro‐2H‐benzo[d][1,3]oxazin‐2‐imines and cis‐N‐phenyl‐hexahydro‐2H‐benzo[d][1,3]thiazin‐2‐imines were prepared and subjected to Flash Vacuum Pyrolysis (FVP). NH− and NCH~3~− oxazines reacted at lower temperatures than the thio‐ analogs, showing lower thermal stability, while NCH~2~Ph− compounds presented the opposite behavior. Oxazines and thiazines yielded different products through homolytic fragmentations of the heterocycle moiety, the stability of which increased with the N− substitution. Based on the analysis of the reaction temperatures and the unraveling of the obtained products, it is proposed that any heterocyclic ring‐opening reactions (initiated by X3−C4, C8a−N1, or C2−X3 bond rupture) require less energy than the retro‐Diels–Alder process (RDA) that yields butadiene. This concerted reaction path is only achieved at temperatures higher than 470 °C. Kinetic measurements reveal negative entropies of activation, which suggest a partially concerted way of reaction or slightly asynchronous fragmentation processes, with higher energy of activation (Ea) values for the N‐substituted derivatives compared to the unsubstituted ones. Experimental result

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Author
Diana C. Pinilla Peña; Elba N. Ruiz Pereyra; Guadalupe Firpo; Noelia M. Ceballos; Ferenc Fülöp; Zsolt Szakonyi; Ana G. Iriarte; Walter J. Peláez
Publisher
Wiley
Published
2021
Language
EN
Field
Chemistry (Physical Sciences)

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Browse all works by Diana C. Pinilla Peña; Elba N. Ruiz Pereyra; Guadalupe Firpo; Noelia M. Ceballos; Ferenc Fülöp; Zsolt Szakonyi; Ana G. Iriarte; Walter J. Peláez