Identification of (−)(E)-N-[2(S)-Hydroxy-2-(4-hydroxyphenyl) ethyl]ferulamide, a Natural Product Isolated from Croton Pullei: Theoretical and Experimental Analysis
Abstract
:1. Introduction
2. Results and Discussion
2.1. Conformational Analysis and Geometric Data
2.2. NMR Spectra and Statistical Analysis
2.3. Infrared Spectrum
2.4. Polarimetry
3. Experimental Section
3.1. Collection and Extraction
3.2. Computational Method
3.3. Statistical Analysis
4. Conclusions
Acknowledgements
References
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B3PW91/DGDZVP | B3LYP/6-31+G(d,p) | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Position | Exp. | Structure O | Structure S | Structure N | Structure O | Structure S | Structure N | ||||||
Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | ||
1 | 128.2 | 131.6 | 3.4 | 129.8 | 1.6 | 131.0 | 2.8 | 125.7 | 2.5 | 124.2 | 4.0 | 126.8 | 1.4 |
2 | 111.0 | 113.4 | 2.3 | 121.0 | 10.0 | 120.3 | 9.3 | 101.9 | 9.0 | 112.1 | 1.1 | 110.7 | 0.3 |
3 | 149.3 | 153.5 | 4.2 | 150.2 | 0.8 | 150.2 | 0.9 | 145.9 | 3.4 | 142.5 | 6.9 | 142.8 | 6.4 |
4 | 149.8 | 154.4 | 4.6 | 154.7 | 4.9 | 153.7 | 3.9 | 146.9 | 2.9 | 147.5 | 2.3 | 144.6 | 5.2 |
5 | 116.4 | 118.3 | 1.9 | 120.9 | 4.5 | 120.6 | 4.2 | 110.2 | 6.2 | 113.2 | 3.2 | 111.9 | 4.5 |
6 | 123.3 | 133.2 | 9.9 | 126.6 | 3.3 | 125.9 | 2.6 | 124.4 | 1.1 | 115.3 | 8.0 | 115.2 | 8.1 |
7 | 142.3 | 155.2 | 12.9 | 148.5 | 6.2 | 152.7 | 10.4 | 143.5 | 1.2 | 137.5 | 4.8 | 141.8 | 0.5 |
8 | 118.6 | 117.0 | 1.6 | 125.3 | 6.7 | 115.4 | 3.2 | 108.0 | 10.6 | 114.4 | 4.2 | 110.9 | 7.6 |
9 | 169.5 | 174.2 | 4.7 | 200.1 | 30.6 | 171.4 | 1.9 | 163.6 | 5.9 | 192.5 | 23.0 | 162.3 | 7.2 |
1′ | 134.7 | 138.7 | 4.0 | 140.7 | 6.0 | 139.4 | 4.7 | 129.2 | 5.5 | 135.2 | 0.5 | 133.3 | 1.4 |
2′ | 128.5 | 133.6 | 5.1 | 136.0 | 7.5 | 132.9 | 4.4 | 125.8 | 2.7 | 123.6 | 4.9 | 124.1 | 4.4 |
3′ | 116.1 | 120.3 | 4.2 | 115.7 | 0.4 | 121.8 | 5.7 | 110.9 | 5.1 | 108.4 | 7.7 | 113.0 | 3.1 |
4′ | 158.1 | 160.3 | 2.3 | 161.6 | 3.4 | 161.9 | 3.8 | 153.4 | 4.7 | 152.6 | 5.5 | 153.7 | 4.4 |
5′ | 116.1 | 116.6 | 0.5 | 121.6 | 5.5 | 116.7 | 0.6 | 108.9 | 7.2 | 111.8 | 4.3 | 109.7 | 6.4 |
6′ | 128.5 | 133.4 | 4.9 | 134.6 | 6.1 | 135.2 | 6.7 | 125.0 | 3.5 | 125.8 | 2.8 | 123.6 | 4.9 |
7′ | 73.4 | 75.1 | 1.7 | 78.6 | 5.2 | 79.4 | 5.9 | 76.2 | 2.8 | 81.7 | 8.3 | 81.9 | 8.6 |
8′ | 48.3 | 75.3 | 26.9 | 47.9 | 0.3 | 55.5 | 7.2 | 74.8 | 26.5 | 50.6 | 2.3 | 53.5 | 5.2 |
OMe | 56.4 | 60.7 | 3.9 | 60.7 | 4.3 | 60.5 | 4.1 | 53.9 | 2.51 | 54.4 | 2.0 | 54.0 | 2.4 |
B3PW91/DGDZVP | B3LYP/6-31+G(d,p) | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Position | Exp. | Structure O | Structure S | Structure N | Structure O | Structure S | Structure N | ||||||
Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | Calc. | RS | ||
2 | 7.11 | 6.97 | 0.14 | 6.83 | 0.28 | 6.83 | 0.28 | 7.19 | 0.08 | 6.61 | 0.50 | 6.78 | 0.33 |
5 | 6.78 | 6.37 | 0.41 | 7.16 | 0.38 | 7.17 | 0.39 | 6.51 | 0.27 | 7.17 | 0.39 | 7.08 | 0.30 |
6 | 7.01 | 6.96 | 0.05 | 7.59 | 0.58 | 7.71 | 0.70 | 6.78 | 0.23 | 7.65 | 0.64 | 7.79 | 0.78 |
7 | 7.43 | 7.66 | 0.23 | 7.63 | 0.20 | 7.90 | 0.47 | 7.88 | 0.45 | 7.79 | 0.36 | 7.89 | 0.46 |
8 | 6.45 | 5.81 | 0.64 | 6.42 | 0.03 | 6.62 | 0.17 | 6.33 | 0.12 | 6.71 | 0.26 | 7.43 | 0.98 |
2′ | 7.22 | 7.28 | 0.06 | 7.12 | 0.10 | 7.80 | 0.58 | 7.28 | 0.06 | 7.04 | 0.18 | 7.81 | 0.59 |
3′ | 6.77 | 7.15 | 0.38 | 6.43 | 0.34 | 7.23 | 0.46 | 7.08 | 0.31 | 6.47 | 0.30 | 7.24 | 0.47 |
5′ | 6.77 | 6.57 | 0.20 | 7.21 | 0.44 | 6.51 | 0.26 | 6.47 | 0.30 | 7.17 | 0.40 | 6.52 | 0.25 |
6′ | 7.22 | 7.84 | 0.62 | 7.88 | 0.66 | 7.19 | 0.03 | 7.51 | 0.29 | 8.20 | 0.98 | 7.09 | 0.13 |
7′ | 4.72 | 4.84 | 0.12 | 4.52 | 0.20 | 4.56 | 0.16 | 5.15 | 0.43 | 5.03 | 0.31 | 4.61 | 0.11 |
8′ a | 3.53 | 4.46 | 0.93 | 2.38 | 1.15 | 2.67 | 0.86 | 3.99 | 0.46 | 2.40 | 1.13 | 2.70 | 0.83 |
8′ b | 3.42 | 4.33 | 0.91 | 3.73 | 0.31 | 3.94 | 0.52 | 4.11 | 0.69 | 3.43 | 0.01 | 3.61 | 0.19 |
Position | 13C | 1H | ||||
---|---|---|---|---|---|---|
Exp. [22] | Calc. | RS | Exp. [22] | Calc. | RS | |
1 | 127.8 | 126.1 | 1.6 | - | - | |
2 | 111.6 | 113.5 | 1.8 | 7.2 | 6.7 | 0.5 |
3 | 151.5 | 145.1 | 6.4 | - | - | |
4 | 149.9 | 145.7 | 4.2 | - | - | |
5 | 116.5 | 111.4 | 5.1 | 6.8 | 6.6 | 0.2 |
6 | 123.9 | 113.6 | 10.4 | 7.5 | 7.5 | 0.4 |
C-α | 115.9 | 107.7 | 8.2 | 6.3 | 6.5 | 0.2 |
C-β | 146.9 | 147.2 | 0.3 | 7.6 | 7.8 | 0.2 |
C=O | 171.2 | 162.7 | 8.5 | - | - | |
OMe-3 | 56.5 | 53.9 | 2.5 | 3.9 | 3.8 | 0.1 |
δ | a | b | R2 | MAE | CMAE | s | PRESS | sPRESS | F | Q2 | |
---|---|---|---|---|---|---|---|---|---|---|---|
B3PW91/DGDZVP | δ(1H) O | 0.80 | 1.41 | 0.90 | 0.39 | 0.40 | 0.4910 | 3.6794 | 0.19 | 86.11 | 84.12% |
δ(1H) S | 1.16 | −0.98 | 0.94 | 0.39 | 0.31 | 0.4182 | 3.0896 | 0.18 | 122.49 | 86.67% | |
δ(1H) N | 1.13 | −0.64 | 0.94 | 0.41 | 0.31 | 0.3856 | 2.6661 | 0.16 | 145.83 | 88.50% | |
δ(13C) O | 0.93 | 13,87 | 0.96 | 5.49 | 4.32 | 6.3579 | 959.879 | 1.94 | 430.88 | 94.69% | |
δ(13C) S | 1.08 | −4.11 | 0.97 | 5.97 | 3.53 | 5.7831 | 913.886 | 1.89 | 524.12 | 94.94% | |
δ(13C) N | 0.98 | 6.86 | 0.99 | 4.57 | 2.21 | 3.2676 | 205.189 | 0.89 | 1675.82 | 98.86% | |
B3LYP/6- 31+G(d,p) | δ(1H) O | 0.86 | 1.00 | 0.96 | 0.31 | 0.25 | 0.2786 | 1.0415 | 0.10 | 222.41 | 94.23% |
δ(1H) S | 1.18 | −1.02 | 0.92 | 0.46 | 0.35 | 0.5231 | 4.6355 | 0.22 | 118.15 | 86.78% | |
δ(1H) N | 1.16 | −0.83 | 0.93 | 0.45 | 0.32 | 0.4879 | 3.8216 | 0.19 | 131.42 | 88.65% | |
δ(13C) O | 0.86 | 14.22 | 0.95 | 5.74 | 5.42 | 6.7773 | 1331.07 | 2.28 | 293.17 | 90.63% | |
δ(13C) S | 1.00 | −1.92 | 0.95 | 5.32 | 4.70 | 7.4911 | 1304.14 | 2.26 | 324.63 | 93.18% | |
δ(13C) N | 0.91 | 7.30 | 0.99 | 4.56 | 2.82 | 3.4479 | 260.415 | 1.01 | 1269.99 | 98.30% | |
δ(1H) FA | 1.02 | −0.12 | 0.95 | 0.26 | 0.24 | 0.3601 | 0.8689 | 0.23 | 71.56 | 91.13% | |
δ(13C) FA | 0.97 | −0.28 | 0.98 | 4.90 | 3.12 | 4.0927 | 179.844 | 1.68 | 498.65 | 97.88% |
Vibrational Mode (cm−1) | Experimental | Theoretical—B3LYP/6-31G(d,p) | Theoretical—B3LYP/6-31+G(d,p) | ||||
---|---|---|---|---|---|---|---|
O structure | S structure | N structure | O structure | S structure | N structure | ||
υ (O-H aliphatic) | 3370 | 3782 | 3808 | 3810 | 3806 | 3633 | 3825 |
υ (O-H aromatic) | 3370 | 3818 | 3760 | 3763 | 3822 | 3765 | 3612 |
υ (N-H) | 3370 | - | - | 3612 | - | - | 3612 |
υ (O-H aromatic) | 3370 | 3822 | 3822 | 3822 | 3828 | 3828 | 3770 |
υa (CH2) + υs (C-H sp2) | - | 3128 | 3156 | 3127 | 3130 | 3137 | 3114 |
υs (CH2) + υs (C-H sp3) + υs (C-H sp2) | - | 3077 | 3089 | 3076 | 3081 | 3098 | 3094 |
υa (CH3) + υ (C-H sp2) | - | 3154 | 3157 | 3155 | 3157 | 3159 | 3157 |
υ (C-H sp2) + υa (C-H sp2 aromatic) | - | 3207 | 3204 | 3206 | 3207 | 3206 | 3201 |
υs (CH3) | - | 3016 | 3026 | 3025 | 3017 | 3029 | 3027 |
υ (C-H sp3) + υs (CH2) | 2930 | 3038 | 3018 | 2985 | 3073 | 3075 | 3064 |
δa (C-H sp2 aromatic) + υs (C-O) | - | 1675 | 1673 | 1673 | 1664 | 1662 | 1662 |
υ (C=O) + υ (C=C trans) + δ(C-H) [+δ(N-H)] a | 1680 | 1794 | 1755 | 1758 | 1768 | 1701 | 1727 |
υs (C=C trans) + υ (C=O) + δ (C-H sp2) or [+ δ(N-H)] a | 1600 | 1691 | 1755 | 1685 | 1679 | 1754 | 1674 |
δa (CH3) | 1510 | 1505 | 1502 | 1502 | 1509 | 1509 | 1510 |
δs (C-H sp2 aromatic) + υ (C-O secondary alcohol) | 1480 | 1307 | 1307 | 1309 | 1311 | 1309 | 1308 |
δs (C-H sp2) + υ (C-O secondary alcohol) | 1390 | 1319 | 1316 | 1319 | 1319 | 1327 | 1318 |
δs (C-H sp2) + δa (CH3) | 1110 | 1225 | 1220 | 1179 | 1220 | 1228 | 1227 |
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Silva, S.d.O.; Peixoto, R.N.S.; Silva, J.R.A.; Alves, C.N.; Guilhon, G.M.S.P.; Santos, L.S.; Brasil, D.d.S.B. Identification of (−)(E)-N-[2(S)-Hydroxy-2-(4-hydroxyphenyl) ethyl]ferulamide, a Natural Product Isolated from Croton Pullei: Theoretical and Experimental Analysis. Int. J. Mol. Sci. 2011, 12, 9389-9403. https://doi.org/10.3390/ijms12129389
Silva SdO, Peixoto RNS, Silva JRA, Alves CN, Guilhon GMSP, Santos LS, Brasil DdSB. Identification of (−)(E)-N-[2(S)-Hydroxy-2-(4-hydroxyphenyl) ethyl]ferulamide, a Natural Product Isolated from Croton Pullei: Theoretical and Experimental Analysis. International Journal of Molecular Sciences. 2011; 12(12):9389-9403. https://doi.org/10.3390/ijms12129389
Chicago/Turabian StyleSilva, Silvana de O., Rosana N.S. Peixoto, José Rogério A. Silva, Cláudio N. Alves, Giselle M.S.P. Guilhon, Lourivaldo S. Santos, and Davi do S.B. Brasil. 2011. "Identification of (−)(E)-N-[2(S)-Hydroxy-2-(4-hydroxyphenyl) ethyl]ferulamide, a Natural Product Isolated from Croton Pullei: Theoretical and Experimental Analysis" International Journal of Molecular Sciences 12, no. 12: 9389-9403. https://doi.org/10.3390/ijms12129389