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Elimination Reactions of Aryl Furylacetates Promoted by R2NH-R2NH2 + in 70 mol% MeCN(aq). Effects of β-Aryl on the Ketene-Forming Transition-State
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  • Elimination Reactions of Aryl Furylacetates Promoted by R2NH-R2NH2 + in 70 mol% MeCN(aq). Effects of β-Aryl on the Ketene-Forming Transition-State
  • Elimination Reactions of Aryl Furylacetates Promoted by R2NH-R2NH2 + in 70 mol% MeCN(aq). Effects of β-Aryl on the Ketene-Forming Transition-State
저자명
Pyun. Sang Yong,Kim. Ju Chang,Cho. Bong Rae
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2014년|35권 7호|pp.2143-2147 (5 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

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 ${eta}$ = 0.37-0.54 and $|{eta}_{lg}|$ = 0.31-0.45. The Br$ddot{o}$nsted ${eta}$ decreased with a poorer leaving group and $|{eta}_{lg}|$ 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 ${eta}$-aryl group on the ketene-forming elimination was assessed.