1334065-25-6Relevant articles and documents
Elimination reactions of (E)-2,4,6-trinitrobenzaldehyde O-aryloximes promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effect of β-aryl group the nitrile-forming transition-state
Pyun, Sang Yong,Byun, Woong Sub,Cho, Bong Rae
body text, p. 1921 - 1924 (2012/01/13)
Nitrile-forming eliminations from (E)-2,4,6-(NO2) 3C6H2CH=NOC6H4-2-X-4- NO2 (1) promoted by R3NH/R3NH+ in 70 mol % MeCN(aq) have been studied kinetically. When X = NO2, the reactions exhibited secondorder kinetics as well as Broensted β = 0.63 and |βlg| = 0.34-0.46, and an E2 mechanism is evident. As the leaving group was made poorer (X = H, Cl, and CF3), Broensted β value increased from 0.63 to 0.85-0.89 without much change in the |βlg| value E2, indicating that structure of the transition state changed to an E1cb-like with extensive Cβ-H bond cleavage, significant negative charge development at the β-carbon, and limited Cα-Oar bond cleavage.