Supporting Information. in 70 mol % MeCN(aq). Effects of β Aryl on the Ketene-Forming Transition-State

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1 Elimination, E2 and E1cb Mechanism, β Aryl Group Effect Bull. Korean Chem. Soc. 2014, Vol. 35, No Supporting Information Elimination Reactions of Aryl Furylacetates Promoted by R 2 NH-R 2 NH 2 in 70 mol % MeCN(aq). Effects of β Aryl on the Ketene-Forming Transition-State Sang Yong Pyun, * Ju Chang Kim, and Bong Rae Cho,* Department of Chemistry, Pukyong National University, Pusan , Korea. * sypyun@pknu.ac.kr Department of Chemistry, Korea University, Seoul , Korea. * chobr@korea.ac.kr Received March 26, 2014, Accepted March 31, 2014 Table S1. Observed Rate Constants for Eliminations from C 4H 3(O)CH 2C(O)OC 6H 3-2-X-4-NO 2 (1a-d) a Promoted by 2,6- DMP/2,6-DMPH 70 mol % MeCN(aq) b,c at 25.0 C Entry 10 2 [Buffer], M 10 3 k obs, -1 d,e s 1a 1b 1c 1d a [Substrate] = M. b Buffer ratio = 1.0. c Ionic strength = 0.1 M (Bu 4N Br - ). d Average of three or more rate constants. e Estimated uncertainty, ± 3%. Table S2. Observed Rate Constants for Eliminations from C 4H 3(O)CH 2C(O)OC 6H 3-2-X-4-NO 2 (1a-d) a Promoted by i- Pr 2NH/i-Pr 2NH 2 b,c 70 mol % MeCN(aq) at 25.0 C Entry 10 2 [Buffer], M 10 3 k obs, -1 d,e s 1a 1a f 1b 1c 1d a [Substrate] = M. b Buffer ratio = 1.0. c Ionic strength = 0.1 M (Bu 4N Br ). d Average of three or more rate constants. e Estimated uncertainty, ± 3%. f Base-solvent = i-pr 2NH/i-Pr 2NH 2 in 70 mol % MeCN-30 mol % D 2O. Table S3. Observed Rate Constants for Eliminations from a C 4H 3(O)CH 2C(O)OC 6H 3-2-X-4-NO 2 (1a-d) a Promoted by i- Bu 2NH/i-Bu 2NH b,c 2 70 mol % MeCN(aq) at 25.0 C Entry 10 2 [Buffer], M 10 3 k obs, -1 d,e s 1a 1b 1c 1d a [Substrate] = M. b Buffer ratio = 1.0. c Ionic strength = 0.1 M (Bu 4N Br ). d Average of three or more rate constants. e Estimated uncertainty, ± 3%. Table S4. Observed Rate Constants for Eliminations from C 4H 3(O)CH 2C(O)OC 6H 3-2-X-4-NO 2(1a-d) a Promoted by Bz(i- Pr)NH/Bz(i-Pr)NH 2 b,c in 70 mol % MeCN(aq) at 25.0 C Entry 10 2 [Buffer], M 10 3 k obs, -1 d,e s 1a 1b 1c 1d a [Substrate] = M. b Buffer ratio = 1.0. c Ionic strength = 0.1 M (Bu 4N Br ). d Average of three or more rate constants. e Estimated uncertainty, ± 3%.

2 2 Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 Sang Yong Pyun et al. Figure S1. Plots of k obs vs base concentration for eliminations from 4-nitrophenyl furylacetate (1a) promoted by 2,6-DMP/2,6- DMPH b,c in 70 mol % MeCN(aq) at ,6-DMP/2,6-DMPH = 1.0, µ = 0.10 M (Bu 4N Br ). The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2(see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S3. Plots of k obs vs base concentration for eliminations from 4-nitrophenyl furylacetate (1a) promoted by Bz(i-Pr)NH/Bz(i- Pr)NH 2 in 70 mol % MeCN(aq) at 25.0 C. Bz(i-Pr)NH/Bz(i- Pr)NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ).The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2 (see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S2. Plots of k obs vs base concentration for eliminations from 4-nitrophenyl furylacetate(1a) promoted by i-bu 2NH/i-Bu 2NH 2 in 70 mol % MeCN(aq) at 25.0 C. i-bu 2NH/i-Bu 2NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ). The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2(see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S4. Plots of k obs vs base concentration for eliminations from 2-methoxy-4-nitrophenyl furylacetate (1b) promoted by 2,6-DMP/ 2,6-DMPH in 70 mol % MeCN(aq) at 25.0 C. 2,6-DMP/2,6- DMPH = 1.0, µ = 0.10 M (Bu 4N Br ).The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2 (see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines).

3 Elimination, E2 and E1cb Mechanism, β Aryl Group Effect Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 3 Figure S5. Plots of k obs vs base concentration for eliminations from 2-methoxy-4-nitrophenyl furylacetate (1b) promoted by i- Pr 2NH/i-Pr 2NH 2 in 70 mol % MeCN(aq) at 25.0 C. i-pr 2NH/i- Pr 2NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ). The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2 (see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S7. Plots of k obs vs base concentration for eliminations from 2-methoxy-4-nitrophenyl furylacetate (1b) promoted by Bz(i-Pr)NH/Bz(i-Pr)NH 2 in 70 mol % MeCN(aq) at 25.0 C. Bz(i-Pr)NH/Bz(i-Pr)NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ). The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2 (see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S6. Plots of k obs vs base concentration for eliminations from 2-methoxy-4-nitrophenyl furylacetate (1b) promoted by i-bu 2NH/ i-bu 2NH 2 in 70 mol % MeCN(aq) at 25.0 C. i-bu 2NH/i-Bu 2NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ). The closed circles are the experimental data and the solid line shows the fitted curve by using eq 2(see text). The curve is dissected into the E2 and E1cb reaction components (dashed lines). Figure S8. Plots of k obs vs base concentration for eliminations from 2-chloro-4-nitrophenyl furylacetate (1c) promoted by R 2NH-R 2NH 2 in 70 mol % MeCN (aq) at 25.0 C. R 2NH- R 2NH 2 = 1.0, m = 0.10 M (Bu 4N Br ). [R 2NH = Bz(i-Pr)NH ( ), i-bu 2NH ( ), 2,6-DMP ( ) ].

4 4 Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 Sang Yong Pyun et al. Figure S9. Plots of k obs vs base concentration for eliminations from 2,4-dinitrophenyl furylacetate (1d) promoted by R 2NH- R 2NH 2 in 70 mol % MeCN(aq) at 25.0 C. R 2NH-R 2NH 2 = 1.0, µ = 0.10 M (Bu 4N Br ). [R 2NH = Bz(i-Pr)NH ( ), i-bu 2NH ( ), 2,6-DMP ( )].

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