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- Title
Flash Vacuum Thermolysis of N-(3- and 4-Pyridylmethylidene)- tert-butylamines: Mechanisms of Formation of Pyrrolopyridines and Naphthyridines.
- Authors
Justyna, Katarzyna; Leśniak, Stanisław; Nazarski, Ryszard B.; Rachwalski, Michał; Vu, Thien Y.; Huynh, Thi Kieu Xuan; Khayar, Saïd; Dargelos, Alain; Chrostowska, Anna; Wentrup, Curt
- Abstract
Pyrrolopyridines and naphthyridines are formed by flash vacuum thermolysis (FVT) of 3- and 4-pyridylmethylidene- tert-butylimines 8 and 15. Elimination of a methyl radical generates resonance stablized 2-azaallyl radicals a1 and b1. The formation of pyrrolopyridines 9, 16 and 17 is rationalized in terms of cyclization of 1-aziridinyl radicals a2 and b2. Formation of naphthyridine 10 from imine 8, and of 11 and 18 from imine 15, are in accord with cyclization of 1-azaallyl radicals a6 and b9. Formation of naphthyridine 11 from 8, and of 10 and 19 from 15, indicate the operation of the spiro-cyclization pathways forming intermediates a9 and b14. Formation of the 1,8-naphthyridine 20 (3 %) indicates a rearrangement through aziridine b22 and biradical b23. DFT calculations at the CAM-B3LYP/6-311G(d,p) level support the proposed reaction mechanisms.
- Subjects
NAPHTHYRIDINES; THERMOLYSIS; METHYL radicals; HETEROCYCLIC compounds; PHOTOELECTRON spectroscopy; DENSITY functionals
- Publication
European Journal of Organic Chemistry, 2014, Vol 2014, Issue 14, p3020
- ISSN
1434-193X
- Publication type
Article
- DOI
10.1002/ejoc.201400112