Table 2.
Assignment of 1H and 13C NMR spectra of dianthocyanins, 1, 5–8 in 5% TFAd-CD3OD.
| 1 | 5 | 6 | 7 | 8 | |||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1H | 13C | 1H | 13C | 1H | 13C | 1H | 13C | 1H | 13C | ||||||||||||
| δ (ppm) | multi. | J (Hz) | δ (ppm) | δ (ppm) | multi. | J (Hz) | δ (ppm) | δ (ppm) | multi. | J (Hz) | δ (ppm) | δ (ppm) | multi. | J (Hz) | δ (ppm) | δ (ppm) | multi. | J (Hz) | δ (ppm) | ||
| Del | 2 | 162.2 | 162.4 | 162.4 | 162.1 | 162.9 | |||||||||||||||
| 3 | 145.9 | 145.8 | 145.9 | 145.9 | 145.9 | ||||||||||||||||
| 4 | 8.60 | s | 131.7 | 8.68 | s | 131.8 | 8.56 | s | 131.7 | 8.61 | s | 131.9 | 8.70 | s | 131.8 | ||||||
| 5 | 156.0 | 156.2 | 155.9 | 156.0 | 159.4 | ||||||||||||||||
| 6 | 6.77 | d | 1.5 | 104.0 | 6.86 | d | 2.5 | 104.1 | 6.72 | brs | 104.3 | 6.75 | br. d | 1.5 | 1041.0 | 6.77 | d | 1.5 | 103.1 | ||
| 7 | 165.5 | 165.7 | 165.5 | 165.6 | 165.6 | ||||||||||||||||
| 8 | 6.98 | brd | 1.5 | 93.1 | 6.70 | br.d | 2.5 | 93.1 | 7.04 | brs | 93.1 | 7.00 | br. s | 93.0 | 7.00 | br. d | 1.5 | 93.5 | |||
| 9 | 154.5 | 154.5 | 154.5 | 154.6 | 154.7 | ||||||||||||||||
| 10 | 112.2 | 112.2 | 112.1 | 112.3 | 112.2 | ||||||||||||||||
| 1’ | 118.5 | 118.6 | 118.4 | 118.7 | 118.4 | ||||||||||||||||
| 2’ | 7.81 | brs | 112.2 | 7.86 | d | 2.5 | 111.8 | 7.85 | brs | 111.9 | 7.88 | br. s | 111.9 | 7.76 | br. s | 112.1 | |||||
| 3’ | 145.0 | 144.8 | 144.9 | 144.8 | 145.9 | ||||||||||||||||
| 4’ | 146.3 | 146.4 | 147.1 | 146.4 | 145.9 | ||||||||||||||||
| 5’ | 145.0 | 144.8 | 144.9 | 144.8 | 145.0 | ||||||||||||||||
| 6’ | 7.81 | brs | 112.2 | 8.29 | dd | 2.5, 8.5 | 112.2 | 7.85 | brs | 111.9 | 7.88 | br. s | 111.9 | 7.76 | br. s | 112.1 | |||||
| G1 | 1 | 5.29 | d | 7.5 | 101.7 | 5.31 | d | 6.5 | 104.1 | 5.24 | d | 7.8 | 101.9 | 5.32 | br.d | 7.5 | 101.5 | 5.24 | d | 7.5 | 102.0 |
| 2 | 3.85 | dd | 7.5, 9.5 | 73.1 | 3.89 | dd | 6.5, 8.0 | 73.2 | 3.80 | dd | 7.8, 9.5 | 73.1 | 3.81 | dd | 7.5, 9.5 | 73.1 | 3.89 | dd | 7.5, 9.5 | 73.1 | |
| 3 | 3.60 | dd | 8.0, 9.5 | 76.4 | 3.61 | dd | 8.0, 9.0 | 76.7 | 3.57 | t | 9.5 | 76.4 | 3.61 | t | 9.5 | 75.8 | 3.60 | dd | 8.0, 9.5 | 76.4 | |
| 4 | 3.54 | t | 9.5 | 69.6 | 3.59 | t | 9.0 | 69.8 | 3.49 | t | 9.5 | 70.0 | 3.55 | t | 9.5 | 69.6 | 3.49 | t | 9.5 | 69.9 | |
| 5 | 3.79 | m | 76.5 | 3.70 | ddd | 2.5, 5.5, 9.0 | 77.8 | 3.78 | m | 76.4 | 3.80 | m | 76.4 | 3.80 | br. dt | 1.5, 9.5 | 76.6 | ||||
| 6a | 4.26 | m | 66.4 | 4.13 | dd | 2.5, 12.0 | 61.2 | 4.27 | brd | 10.5 | 66.7 | 4.28 | dd | 9.5, 12.0 | 66.4 | 4.20 | br. dd | 1.5, 12.0 | 66.6 | ||
| 6b | 3.79 | m | 3.98 | dd | 5.5, 12.0 | 3.80 | m | 3.80 | m | 3.73 | br. d | 9.5,12.0 | |||||||||
| G2 | 1 | 5.19 | d | 7.5 | 100.4 | 5.18 | d | 7.5 | 100.3 | 5.21 | d | 7.8 | 100.0 | 5.20 | br. d | 7.5 | 100.4 | 4.92 | d | 7.5 | 99.9 |
| 2 | 3.73 | dd | 7.5, 9.5 | 72.8 | 3.72 | dd | 7.5, 9.0 | 72.8 | 3.72 | dd | 7.8, 9.5 | 72.8 | 3.74 | br. dd | 7.5, 9.5 | 72.8 | 3.67 | dd | 7.5, 9.5 | 76.2 | |
| 3 | 3.60 | t | 9.5 | 75.8 | 3.58 | t | 9.0 | 76.3 | 3.59 | t | 9.5 | 76.3 | 3.61 | br. t | 9.5 | 76.3 | 3.59 | t | 9.5 | 76.5 | |
| 4 | 3.49 | t | 9.5 | 70.7 | 3.48 | t | 9.0 | 69.7 | 3.47 | t | 9.5 | 71.8 | 3.49 | br. t | 9.5 | 70.7 | 3.46 | t | 9.5 | 70.7 | |
| 5 | 3.99 | ddd | 2.0, 9.5, 10.0 | 74.6 | 3.95 | ddd | 2.5, 5.5, 9.0 | 74.6 | 4.00 | m | 74.7 | 4.03 | br. ddd | 2.0, 9.5, 10.0 | 74.6 | 3.91 | br. m | 74.6 | |||
| 6a | 4.73 | dd | 10.0, 12.0 | 64.4 | 4.74 | dd | 2.5, 12.0 | 64.4 | 4.75 | d | 12.0 | 64.4 | 4.67 | br. dd | 10.0, 12.0 | 64.6 | 4.26 | dd | 10.0, 12.0 | 63.9 | |
| 6b | 4.37 | dd | 2.0, 12.0 | 4.36 | dd | 5.5, 12.0 | 4.37 | dd | 9.0, 12,0 | 4.42 | br. dd | 2.0, 12.0 | 4.83 | dd | 2.0, 12.0 | ||||||
| G3 | 1 | 4.92 | d | 7.5 | 100.5 | 4.96 | d | 7.5 | 100.4 | 4.93 | d | 7.5 | 100.5 | 5.01 | br. d | 7.5 | 99.3 | 4.92 | d | 7.5 | 100.7 |
| 2 | 3.61 | dd | 7.5, 9.5 | 73.2 | 3.61 | dd | 7.5, 9.0 | 73.0 | 3.61 | dd | 7.5, 9.5 | 73.2 | 3.56 | br. dd | 7.5, 9.5 | 73.0 | 3.61 | dd | 7.5, 9.5 | 73.2 | |
| 3 | 3.70 | t | 9.5 | 76.1 | 3.69 | t | 9.0 | 76.2 | 3.71 | t | 9.5 | 76.2 | 3.70 | br. t | 9.5 | 76.6 | 3.70 | t | 9.5 | 73.0 | |
| 4 | 3.38 | t | 9.5 | 71.6 | 3.39 | t | 9.0 | 71.4 | 3.97 | t | 9.5 | 71.6 | 3.37 | br. t | 9.5 | 71.6 | 3.38 | t | 9.5 | 71.2 | |
| 5 | 3.80 | m | 73.5 | 4.00 | ddd | 2.5, 5.5, 9.0 | 73.3 | 3.97 | m | 73.6 | 4.00 | br. m | 73.3 | 3.93 | m | 73.9 | |||||
| 6a | 4.73 | brd | 2.5, 12.0 | 64.4 | 4.80 | dd | 2.5, 12.0 | 64.5 | 4.75 | brd | 11.0 | 64.3 | 4.77 | br. dd | 2.5, 12.0 | 64.5 | 4.71 | br. d | 2.5, 12.0 | 63.7 | |
| 6b | 3.80 | m | 3.95 | dd | 5.5, 12.0 | 4.02 | brd | 11.0 | 3.91 | br. m | 4.38 | dd | 9.0, 12.0 | ||||||||
| G4 | 1 | 4.60 | d | 7.5 | 101.4 | 4.53 | d | 7.5 | 101.6 | 4.73 | d | 7.8 | 99.7 | 4.57 | br. d | 7.5 | 101.0 | ||||
| 2 | 3.47 | dd | 7.5, 9.5 | 73.3 | 3.49 | dd | 7.5, 9.0 | 73.3 | 3.44 | dd | 7.8, 9.5 | 72.7 | 3.46 | br. dd | 7.5, 9.5 | 73.2 | |||||
| 3 | 3.60 | t | 9.5 | 76.3 | 3.60 | t | 9 | 75.8 | 3.56 | t | 9.5 | 76.5 | 3.61 | br. t | 9.5 | 76.5 | |||||
| 4 | 3.46 | t | 9.5 | 69.8 | 3.48 | t | 9 | 70.7 | 3.47 | m | 70.0 | 3.50 | br. t | 9.5 | 69.8 | ||||||
| 5 | 3.50 | m | 76.5 | 3.43 | ddd | 2.5, 5.5, 9.0 | 76.4 | 3.47 | m | 76.3 | 3.48 | br. m | 76.3 | ||||||||
| 6a | 3.85 | dd | 2.0, 12.0 | 60.8 | 3.80 | dd | 2.5,12.5 | 60.6 | 3.89 | dd | 1.5, 11.0 | 61.0 | 3.83 | br. dd | 2.0, 12.0 | 60.7 | |||||
| 6b | 3.75 | dd | 4.5, 12.0 | 3.75 | dd | 5.5, 12.5 | 3.75 | brd | 11.0 | 3.77 | br. dd | 4.5, 12.0 | |||||||||
| Rha | 1 | 4.89 | brd | 1.0 | 101.7 | 4.86 | brs | 100.9 | 4.87 | br. s | 101.1 | 4.81 | br. d | 1.0 | 101.7 | ||||||
| 2 | 4.09 | dd | 1.0, 3.5 | 70.3 | 4.05 | brdd | 1.5, 3.0 | 70.4 | 4.11 | br. d | 3.5 | 70.3 | 4.01 | dd | 1.0, 3.5 | 70.3 | |||||
| 3 | 3.72 | dd | 3.5, 9.5 | 71.2 | 3.75 | dd | 3.0, 9.5 | 71.2 | 3.72 | dd | 3.5, 9.5 | 71.2 | 3.74 | dd | 3.5, 9.5 | 71.2 | |||||
| 4 | 3.40 | t | 9.5 | 72.5 | 3.43 | t | 9.5 | 69.8 | 3.40 | t | 9.5 | 72.5 | 3.40 | t | 9.5 | 72.5 | |||||
| 5 | 3.67 | dt | 6.0, 9.5 | 70.3 | 3.65 | dt | 6.5, 9.5 | 68.6 | 3.66 | m | 68.6 | 3.65 | dt | 6.0, 9.5 | 68.5 | ||||||
| 6 | 1.26 | d | 6.0 | 16.5 | 1.28 | d | 6.5 | 16.6 | 1.25 | dd | 6.0 | 16.5 | 1.25 | d | 6.0 | 16.5 | |||||
| acyl1 | 1 | 128.7 | 128.6 | 128.6 | 127.8 | 128.7 | |||||||||||||||
| 2 | 6.80 | d | 2.5 | 116.9 | 6.88 | d | 2.5 | 116.9 | 6.87 | d | 1.5 | 116.5 | 7.33 | br. d | 8.5 | 129.4 | 6.80 | d | 2.5 | 115.9 | |
| 3 | 146.3 | 146.4 | 146.5 | 6.82 | br. d | 8.5 | 115.9 | 146.4 | |||||||||||||
| 4 | 147.1 | 147.2 | 147.1 | 159.2 | 147.1 | ||||||||||||||||
| 5 | 6.72 | d | 8.5 | 115.1 | 6.79 | d | 8.5 | 115.0 | 6.75 | d | 8.5 | 115.3 | 6.82 | br. d | 8.5 | 119.9 | 6.73 | d | 8.5 | 115.3 | |
| 6 | 6.67 | dd | 2.5, 8.5 | 118.4 | 6.86 | dd | 2.5, 8.5 | 118.0 | 6.73 | dd | 1.5, 8.5 | 118.4 | 7.33 | br. d | 8.5 | 129.4 | 6.51 | dd | 2.5, 8.5 | 119.1 | |
| α | 5.84 | d | 15.5 | 115.2 | 6.50 | d | 15.5 | 118.5 | 6.45 | d | 16.0 | 115.0 | 6.55 | d | 16.0 | 114.7 | 6.28 | d | 15.5 | 115.3 | |
| β | 7.13 | d | 15.5 | 144.7 | 7.55 | d | 15.5 | 145.2 | 7.53 | d | 16.0 | 145.3 | 7.64 | d | 16.0 | 144.9 | 7.38 | d | 15.5 | 144.9 | |
| CO | 167.5 | 167.4 | 167.3 | 167.7 | 167.3 | ||||||||||||||||
| acyl2 | 1 | 129.1 | 128.7 | 128.0 | 129.0 | 126.0 | |||||||||||||||
| 2 | 6.64 | d | 2.5 | 113.6 | 6.91 | d | 2.5 | 113.6 | 7.09 | d | 8.5 | 128.6 | 6.78 | br. s | 113.5 | 6.80 | d | 2.5 | 113.5 | ||
| 3 | 146.8 | 145.8 | 6.72 | d | 8.5 | 116.4 | 146.6 | 146.2 | |||||||||||||
| 4 | 146.7 | 146.8 | 158.8 | 146.8 | 147.8 | ||||||||||||||||
| 5 | 6.63 | d | 8.5 | 115.8 | 6.68 | d | 8.5 | 115.6 | 6.72 | d | 8.5 | 116.4 | 6.55 | br. d | 8.5 | 115.3 | 6.49 | d | 8.5 | 115.0 | |
| 6 | 6.57 | dd | 2.5, 8.5 | 120.4 | 6.47 | dd | 2.5, 8.5 | 121.0 | 7.09 | d | 8.5 | 128.6 | 6.32 | br. d | 8.5 | 120.4 | 6.54 | dd | 2.5, 8.5 | 121.2 | |
| α | 5.77 | d | 15.5 | 116.9 | 6.16 | d | 15.5 | 116.9 | 6.14 | d | 16.0 | 116.5 | 6.12 | d | 16.0 | 117.0 | 6.09 | d | 15.5 | 114.1 | |
| β | 6.99 | d | 15.5 | 143.2 | 7.01 | d | 15.5 | 143.4 | 7.12 | d | 16.0 | 143.0 | 6.90 | br. d | 16.0 | 143.0 | 7.21 | d | 15.5 | 144.8 | |
| CO | 166.8 | 167.0 | 166.9 | 166.9 | 167.3 | ||||||||||||||||