9.4 6.60. 8.6 8.8 9.29 20.04 29.6 0.07 6. 40.92 4.64 06.0 6.29 6.0-0.00 Supplementary Information Conformational Analysis, Experimental and GIA-DFT C NMR Chemical Shift Calculation on 2 -Hydroxy-,4,-trimethoxy-chalcone Fabio Luiz P. Costa, a Paulo F. Gomes, b Andressa K. Silva c and Luciano M. Lião*,c a Departamento de Química and b Departamento de Física, Universidade Federal de Goiás, BR 64, km 92, 800, 780-6 Jataí-G, Brazil c Instituto de Química, Universidade Federal de Goiás, Av. Esperança s/n, Campus Samambaia, 74690-900 Goiânia-G, Brazil ' H 90 80 70 60 0 40 0 20 0 00 90 80 70 60 0 40 0 20 0 ppm Figure S. C NMR spectrum (2.7 MHz, CDCl ) of 2 -hydroxy-,4,-trimethoxy-chalcone. *e-mail: fabbioquimica@gmail.com; lucianoliao@ufg.br
ppm 0 60 ' 70 H 80 90 00 0 20 0 40 0 8.0 7. 7.0 6. 6.0..0 4. 4.0 ppm Figure S2. HSQC NMR contour map (00 MHz, CDCl ) of 2 -hydroxy-,4,-trimethoxy-chalcone. ppm 20 ' 40 H 60 80 00 20 40 60 80 200 220 2 0 9 8 7 6 4 ppm Figure S. HMBC NMR contour map (00 MHz, CDCl ) of 2 -hydroxy-,4,-trimethoxy-chalcone.
H ' A H H 2 N ' B Me Figure S4. Structure of (E)--(4-hydroxy--methoxyphenyl)--(,-di-tert-butyl-4-hydroxyphenyl)prop-2-en- -one (A) and (E)--(4-aminophenyl)--(,4-dimethoxyphenyl)prop-2-en--one (B). Figure S. Superposition of the four lowest energy conformations of (E)--(4-hydroxy--methoxyphenyl)- -(,-di-tert-butyl-4-hydroxyphenyl)prop-2-en--one molecule.
Figure S6. DFT-optimized structures of the four more stable conformers,, 2, and 4, respectively, of (E)--(4-hydroxy--methoxyphenyl)--(,-di-tert-butyl-4-hydroxyphenyl)prop-2-en--one. For relative energies and abundances of the conformers, see Table S. Figure S7. Superposition of the five lowest energy conformations of (E)--(4-aminophenyl)- -(,4-dimethoxyphenyl)prop-2-en--one molecule.
Figure S8. DFT-optimized structures of the five more stable conformers,, 2,, 4 and, respectively, of (E)--(4-aminophenyl)--(,4-dimethoxyphenyl)prop-2-en--one. For relative energies and abundances of the conformers, see Table S.
Table S. DFT, thermo chemical parameter and DFT population for the 7 more significant conformations of (E)--(4-hydroxy--methoxyphenyl)--(,-di-tert-butyl-4-hydroxyphenyl)prop-2-en--one Conformer ΔE a / Bolt. ΔE c / Bolt. ΔE e / Bolt. ΔG g / Bolt. (kcal mol - ) dist. b / % (kcal mol - ) dist. d / % (kcal mol - ) dist. f / % (kcal mol - ) dist. h / % 00 0.00 49 0.00 7.4 0.00.4 0.00 6.4 002 0. 4 0.68 20.4 0.6 9.9 0.44 29.0 00.28.6.29 6.6.42.9.6.7 004..7 2.4 0.7.79 2.0.9 2.0 00.07 0. 2.8 0.4 2.60 0.4 006. 0.2 2.94 0. 2.6 0.4 007.79 0..78 0. 008 4. 0.0.79 0. 009 6.24 0.0 4.06 0.0 00 6.0 0.0 0 7.80 0.0 02 8.0 0.0 0 8.79 0.0 04 8.9 0.0 0 8.97 0.0 06 9.08 0.0 07 9.9 0.0 a Relative MMFF energy of conformers obtained from Monte Carlo analysis; b MMFF Boltzmann population of the conformers; c relative BLYP/6-G(d) single point energy of conformers obtained from Monte Carlo analysis; d BLYP/6-(g) single point energy Boltzmann population of the conformers; e relative mpwpw9/ 6-G(d) energy minimization of the conformers; f mpwpw9/6-g(d) energy minimization Boltzmann population of the conformers; g relative mpwpw9/6-g(d) sum of electronic and free energy of the conformers; h mpwpw9/6-g(d) Boltzmann population calculated from ΔG values of the conformers.
Table S2. Calculated (scaled) and differences between experimental C NMR chemical shifts (in ppm) in the (E)--(4-hydroxy--methoxyphenyl)--(,-di-tert-butyl-4-hydroxyphenyl)prop-2-en--one relative to TMS, for approaches (I) and (II) Nuclei δ exp Approach (I) Approach (II) δ a calc (δ scal ) b δ calc (δ scal ) δ a calc (δ scal ) b δ calc (δ scal ) C 26.4 2.6 (26.) 4.79 (0.07) 20.8 (2.6).7 ( 0.7) *C2 2.8 20. (2.).2 (-0.4) 20. (2.).0 ( 0.7) *C 6.. (6.9) 4.97 (0.8) 0.9 (6.2).62 ( 0.29) C4 6.4. (7.).28 (.06) 0.7 (7.0).74 (0.7) *C 6.. (6.9).2 (0.8) 0.9 (6.2).62 ( 0.29) *C6 2.8 20. (2.).26 ( 0.4) 20. (2.).0 ( 0.7) **C7 4.4 6.2 (6.8).8 (2.44) 4. (.0) 0.09 (0.9) **C8 0.2. (.7).4 (.49) 29. (29.8) 0.68 ( 0.4) α 8.8 0.7 (.) 8.06 (.74) 09.9 (7.) 8.9 (.67) β 4.6 42.2 (48.).8 (2.) 4. (47.4) 4.06 (.79) β 89 7.8 (8.4).8 (.6) 7.6 (8.2).8 (.82) C. 2.7 (0.8).80 ( 0.7) 24.9 (0.0) 6.6 (.) C2 2. 9.0 (2.8) 4.48 (0.2) 8.0 (22.7).47 ( 0.79) C.7 09.0 (.2) 4.68 ( 0.4) 08.0 (2.2).72 (.4) C4 0. 44. (0.) 6.00 ( 0.0) 4.6 (49.) 6.4 ( 0.8) C 46.9 8.9 (44.6) 8.02 ( 2.29) 8. (44.0) 8.6 ( 2.86) C6 0.6 08. (2.) 2.47 (.72) 07. (.).29 (0.86) - 6. 4.7 (6.2).4 (0.06). (4.).00 (.6) a Calculated chemical shifts (δ calc = σ TMS σ aver or σ lowe ) obtained by TMS subtraction; b scaled chemical shifts (δ scal =.0δ calc.22) obtained by the generated universal scaling factor. *The δ calc and δ scal for C2 and C6, C and C were arithmetically averaged; **the δ calc and δ scal for C7 and C8, were arithmetically averaged from the two t-butyl carbons and of the methyl carbons of the two t-butyl ligands, respectively.
Table S. DFT, thermo chemical parameter and DFT population for the more significant conformations of (E)--(4-aminophenyl)--(,4-dimethoxyphenyl)prop-2-en--one Conformer ΔE a / Bolt. ΔE c / Bolt. ΔE e / Bolt. ΔG g / Bolt. (kcal mol - ) dist. b / % (kcal mol - ) dist. d / % (kcal mol - ) dist. f / % (kcal mol - ) dist. h / % 00 0.00 20. 0.00 7.4 0.00.4 0.00 69. 002 0.08 7.8 0.68 20.4 0.6 9.9 0.99.2 00 0..9.29 6.6.42.9.00.0 004 0.7.4 2.4 0.7.79 2.0.44 4.8 00 0.27 2.9 2.8 0.4 2.60 0.4.9.9 006 0.4 0. 2.94 0. 2.6 0.4 007 0.89 4.6.78 0. 008.7 2.0.79 0. 009.6 0. 4.06 0.0 00.8 0. 0.26 0. 02.29 0. 0.7 0. 04.69 0.0 0 4.6 0.0 a Relative MMFF energy of conformers obtained from Monte Carlo analysis; b MMFF Boltzmann population of the conformers; c relative BLYP/6-G(d) single point energy of conformers obtained from Monte Carlo analysis; d BLYP/6-(g) single point energy Boltzmann population of the conformers; e relative mpwpw9/ 6-G(d) energy minimization of the conformers; f mpwpw9/6-g(d) energy minimization Boltzmann population of the conformers; g relative mpwpw9/6-g(d) sum of electronic and free energy of the conformers; h mpwpw9/6-g(d) Boltzmann population calculated from ΔG values of the conformers.
Table S4. Calculated (scaled) and differences between experimental ¹³C NMR chemical shifts (in ppm) in the (E)--(4-aminophenyl)--(,4-dimethoxyphenyl)prop-2-en--one relative to TMS, for approaches (I) and (II) Nuclei δ exp Approach (I) Approach (II) δ a calc (δ scal ) b δ calc (δ scal ) δ a calc (δ scal ) b δ calc (δ scal ) C 28.0 2.62 (28.8) 4.9 (0.7) 22.06 (26.9).9 (.06) C2 2.2 7.7 (22.40).9 (.08).09 (7.) 8.2 (.79) C.0 07.42 (.7).68 (.) 0.67 (09.7) 7.4 (.7) C4.4 44.76 (0.78) 6.8 ( 0.6) 4.88 (49.8) 7.46 (.49) C 49.29 4.0 (49.0) 6.9 ( 0.26) 4.94 (47.8) 7. (.48) C6 4. 4.49 (8.99) 0.04 (4.46). (.86).02 (.) Cα 22.8. (7.) 9.74 (.0).6 (.70).49 ( 7.) Cβ 4.0 4.0 (46.84) 4.29 (.4) 40.28 (46.07).02 (0.77) C9 88.97 7.87 (8.44).0 (.) 7.4 (82.96).6 ( 6.0) C.7 24.7 (29.77). (.) 2.6 (28.2) 8.9 (.2) *C2.8 26.8 (.69) 7 (.98) 26.8(.69) (0.) *C 4.6 08.86 (.09) (0.) 07.0 (.44) 7.06 ( 2.92) C4.9 42.64 (48.) 2. ( 6.64) 4.68 (47.). ( 7.64) *C 4.6 08.86 (.09).0 (.27) 07.0 (.44) 7.06 ( 2.92) *C6.8 26.8 (.69) (0.) 26.8 (.69) (0.) - 6.0.86 (7.4) 0. (.42) 2.7 (4.7).26 (.84) -4 6.0.86 (7.4) 0. (.42) 2.7 (4.7).26 (.84) a Calculated chemical shifts (δ calc = σ TMS σ aver or σ lowe ) obtained by TMS subtraction; b scaled chemical shifts (δ scal =.0δ calc.22) obtained by the generated universal scaling factor. *The δ calc and δ scal for C2 and C6, C and C were arithmetically averaged. Reference. Costa, F. L. P.; de Albuquerque, A. C. F.; Borges, R. M.; dos Santos Jr., F. M.; de Amorim, M. B.; J. Comput. Theor. Nanosci. 204,, 29.