title: Functional group transformations in derivatives of 1,4-dihydrobenzo[1,2,4]triazinyl radical.
abstract: Transformations of functional groups OCOPh, OCH2Ph, I, NO2, and CO2Me in Blatter's radical derivatives 1-5 were investigated in order to develop synthetic tools for incorporation of the benzo[1,2,4]triazinyl system into complex molecular architectures. Thus, basic hydrolysis of OCOPh or Pd-catalyzed debenzylation of OCH2Ph gave phenol functionality, which was acylated and alkylated. Pd-catalyzed Suzuki, Negishi, Sonogashira, and Heck C-C cross-coupling reactions of iodo derivatives 1c, 1d, and 2d were also successful and efficient. Reduction of NO2 in 1e led to aniline derivative 1t, which was reductively alkylated with hexanal and coupled to l-proline. Selected benzo[1,2,4]triazinyl radicals were characterized by EPR and electronic absorption spectroscopy, and the results were analyzed in tandem with DFT computational methods. Lastly, the mechanism for formation of the 1,4-dihydrobenzo[1,2,4]triazine ring was investigated using the B3LYP/6-31G(2d,p) method.
authors: Organic Materials Research Group Department of Chemistry, Vanderbilt University , Nashville, Tennessee 37235, United States.
authors: Agnieszka
authors: A
authors: Bodzioch
authors: Minyan
authors: M
authors: Zheng
authors: Piotr
authors: P
authors: Kaszyński
authors: Greta
authors: G
authors: Utecht
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry; D002384:Catalysis; D005609:Free Radicals / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D011789:Quantum Theory; D014227:Triazines / Q000737:chemistry*
chemical_list: D000814:Aniline Compounds; D005609:Free Radicals; D014227:Triazines; D010165:Palladium