Elimination Reactions of Aryl Furylacetates Promoted by R₂NH-R₂NH₂ ⁺ in 70 mol% MeCN(aq). Effects of β-Aryl on the Ketene-Forming Transition-State

다국어 초록 (Multilingual Abstract)

Ketene-forming elimination from 2-X-4-nitrophenyl furylacetates (1a-d) promoted by $R_2NH-R_2NH_2{^+}$ in 70 mol % MeCN(aq) has been studied kinetically. When X = Cl and $NO_2$, the reactions exhibited second-order kinetics as well as Br$\ddot{o}$nsted ${\beta}$ = 0.37-0.54 and $|{\beta}_{lg}|$ = 0.31-0.45. The Br$\ddot{o}$nsted ${\beta}$ decreased with a poorer leaving group and $|{\beta}_{lg}|$ increased with a weaker base. The results are consistent with an E2 mechanism. When the leaving group was changed to a poorer one [X= H (1a) and $OCH_3$ (1b)], the reaction mechanism changed to the competing E2 and E1cb mechanisms. A further change to the E1cb mechanism was realized for the reaction of 1a with $i-Pr_2NH/i-Pr_2NH_2{^+}$ in 70 mol % MeCN-30 mol % $D_2O$. By comparing the kinetic results in this study with the existing data for $ArCH_2C(O)OC_6H_3-2-X-4-NO_2$, the effect of the ${\beta}$-aryl group on the ketene-forming elimination was assessed.