Table 1. 1H (600 MHz) and 13C (150 MHz) NMR Spectral Data for Hydroxycinnamoylagmatine Dimers in Methanol-d4; Assignments Were Based on HMBC and HSQC 2D Spectra.
| product |
||||||||
|---|---|---|---|---|---|---|---|---|
| CouAgm-4-O-7′/3-8′-DCouAgm
(9) |
FerAgm-8-8′-FerAgm (12)a |
FerAgm-2-7′/8-8′-DFerAgm
(13) |
FerAgm-4-O-7′/3-8′-DFerAgm
(18) |
|||||
| position | δC | δH, mult. (J)b | δC | δH, mult. (J) | δC | δH, mult. (J) | δC | δH, mult. (J) |
| 1 | 128.16 | 127.03 | 123.71 | 129.10 | ||||
| 2 | 124.20 | 7.38 (1H, s) | 112.08 | 7.25 (2H, d, 1.74) | 131.39 | 111.58 | 7.19 (1H, s) | |
| 3 | 127.44 | 147.72 | 115.54 | 6.45 (1H, s) | 145.00 | |||
| 4 | 161.30 | 148.12 | 148.41 | 150.20 | ||||
| 5 | 109.78 | 6.91 (1H, d, 8.50) | 115.15 | 6.82 (2H, d, 8.29) | 146.75 | 144.86 | ||
| 6 | 129.04 | 7.53 (1H, d, 8.65) | 124.53 | 7.10 (2H, dd, 8.39, 1.74) | 111.72 | 6.96 (1H, s) | 116.98 | 7.00 (1H, s) |
| 7 | 140.10 | 7.50 (1H, d, 15.39) | 140.78 | 7.90 (2H, s) | 132.89 | 7.30 (1H, s) | 140.42 | 7.48 (1H, d, 15.71) |
| 8 | 117.70 | 6.48 (1H, d, 15.39) | 126.66 | 127.52 | 118.12 | 6.49 (1H, d, 15.38) | ||
| 9 | 167.80 | 166.79 | 169.63 | 167.77 | ||||
| 11 | 38.50 | 3.37 (4H, m)c | 38.44 | 3.44 (4H, m) | 38.60 | 3.29 (2H, m) | 38.45 | 3.37 (2H, m) |
| 12 | 25.76 | 1.66 (4H, m) | 25.79 | 1.61 (6H, m) | 25.80 | 1.31 (2H, m) | 25.78 | 1.66 (4H, m) |
| 13 | 26.33 | 1.66 (4H, m) | 25.79 | 1.61 (6H, m) | 25.80 | 1.31 (2H, m) | 25.78 | 1.66 (4H, m) |
| 14 | 40.75 | 3.24 (4H, m)d | 40.73 | 3.21 (4H, m) | 40.70 | 3.21 (2H, m) | 40.60 | 3.24 (2H, m) |
| 16 | 157.70 | 157.19 | 157.27 | 157.28 | ||||
| MeO-C3 | 54.94 | 3.80 (6H, s) | 55.32 | 3.90 (3H, s) | 55.47 | 3.94 (3H, s) | ||
| MeO-C5 | ||||||||
| 1′ | 130.80 | 133.75 | 131.20 | |||||
| 2′ | 127.06 | 7.20 (2H, d, 8.50) | 120.66 | 6.53 (1H, dd, 7.88, 1.64) | 109.10 | 6.96 (1H, s) | ||
| 3′ | 115.23 | 6.82 (2H, d, 8.94) | 147.72 | 147.96 | ||||
| 4′ | 157.32 | 145.04 | 146.88 | |||||
| 5′ | 115.23 | 6.82 (2H, d, 8.94) | 114.72 | 6.71 (1H, d, 8.18) | 115.04 | 6.83 (2H, s) | ||
| 6′ | 127.06 | 7.20 (2H, d, 8.50) | 111.72 | 6.78 (1H, d, 1.74) | 118.60 | 6.83 (2H, s) | ||
| 7′ | 88.10 | 5.93 (1H, d, 7.77) | 47.06 | 4.34 (1H, d, 6.96) | 88.80 | 6.97 (1H, d, 8.35) | ||
| 8′ | 56.60 | 4.20 1H, d, 7.58) | 50.37 | 3.78 (1H, d, 6.85) | 57.60 | 4.24 (1H, d, 8.02) | ||
| 9′ | 172.10 | 173.93 | 171.80 | |||||
| 11′ | 38.50 | 3.36 (4H, m)c | 38.35 | 3.06 (2H, m) | 38.60 | 3.34 (2H, m) | ||
| 12′ | 25.76 | 1.63 (4H, m) | 25.80 | 1.31 (2H, m) | 26.44 | 1.63 (4H, m) | ||
| 13′ | 26.33 | 1.63 (4H, m) | 25.80 | 1.31 (2H, m) | 26.44 | 1.63 (4H, m) | ||
| 14′ | 40.75 | 3.23 (4H, m)c | 40.73 | 2.97 (2H, m) | 40.68 | 3.23 (2H, m) | ||
| 16′ | 157.70 | 157.27 | 157.28 | |||||
| MeO-C3′ | 54.96 | 3.81 (3H, s) | 55.06 | 3.85 (3H, s) | ||||
| MeO-C5′ | ||||||||
| product |
||||||||
|---|---|---|---|---|---|---|---|---|
| FerAgm-4-O-8′-FerAgm (21) |
SinAgm-2-7′/8–8′-SinAgm (25) |
SinAgm-8-8′-SinAgm (27)a |
SinAgm-8-8′/9-N-7′-DSinAgm
(29) |
|||||
| position | δC | δH, mult. (J) | δC | δH, mult. (J) | δC | δH, mult. (J) | δC | δH, mult. (J) |
| 1 | 130.6 | n.d. | 126.06 | 125.29 | ||||
| 2 | 111.07 | 7.32 (1H, d, 1.49) | 123.36 | 107.23 | 6.96 (4H, s) | 107.49 | 6.77 (2H, s) | |
| 3 | 149.23 | 145.4 | 147.95 | 148.01 | ||||
| 4 | 146.45 | 141.47 | 137.35 | 136.03 | ||||
| 5 | 113.7 | 6.81 (1H, d, 8.44) | 147.84 | 147.95 | 148.01 | |||
| 6 | 121.07 | 7.05 (1H, dd, 8.51, 1.62) | 108.06 | 7.03 (1H, s) | 107.23 | 6.96 (4H, s) | 107.49 | 6.77 (2H, s) |
| 7 | 139.78 | 7.47 (1H, d, 15.94) | 134.18 | 7.57 (1H, s) | 140.98 | 7.92 (2H, s) | 134.99 | 7.53 (1H, d, 2.40) |
| 8 | 119.6 | 5.63 (1H, d, 15.87) | 125.7 | 127.43 | 126.2 | |||
| 9 | 167.9 | 168.91 | 166.7 | 169.75 | ||||
| 11 | 38.52 | 3.37 (3H, m)d | 38.71 | 3.30 (4H, m)d | 38.7 | 3.45 (2H, m) | 38.69 | 3.24 (2H, m) |
| 12 | 25.67 | 1.56 (2H, m) | 25.87 | 1.34 (2H, m) | 25.35 | 1.64 (2H, m) | 25.6 | 1.57 (4H, m) |
| 13 | 26.35 | 1.65 (4H, m) | 25.93 | 1.64 (2H, m) | 26.4 | 1.21 (4H, m) | 36.34 | 1.37 (4H, m) |
| 14 | 40.68 | 3.24 (2H, m) | 40.66 | 3.19 (5H, m) | 40.8 | 2.95 (4H, m) | 40.63 | 3.20 (4H, m) |
| 16 | 157.25 | 157.38 | 157.25 | 157.23 | ||||
| MeO-C3 | 55.18 | 4.03 (3H, s) | 74.6 | 3.58 (3H, s) | 55.4 | 3.83 (12H, s) | 55.71 | 3.87 (6H, s) |
| MeO-C5 | 70.5 | 3.94 (3H, s) | 55.4 | 3.83 (12H, s) | 55.71 | 3.87 (6H, s) | ||
| 1′ | 124.05 | 133.67 | 130.1 | |||||
| 2′ | 112.4 | 7.33 (1H, d, 1.69) | 104.72 | 6.41 (2H, s) | 103.67 | 6.57 (2H, s) | ||
| 3′ | 147.55 | 147.56 | 148.53 | |||||
| 4′ | 148.08 | n.d. | 137.4 | |||||
| 5′ | 114.08 | 6.75 (1H, d, 8.17) | 147.56 | 148.53 | ||||
| 6′ | 124.9 | 7.07 (1H, dd, 8.24, 1.76) | 104.72 | 6.41 (2H, s) | 103.67 | 6.57 (2H, s) | ||
| 7′ | 123.89 | 7.27 (1H, s) | 40.52 | 4.87 (2H, s)d | 65.67 | 4.64 (n.d., d, 3.26)d | ||
| 8′ | 140.5 | 48.68 | 3.85 (1H, d, 1.40) | 53.28 | 4.00 (1H, m) | |||
| 9′ | 164.62 | 173.13 | 171.8 | |||||
| 11′ | 38.52 | 3.35 (n.d., m)d | 38.21 | 3.07 (2H, m) | 38.8 | 3.13 (2H, m) | ||
| 12′ | 25.67 | 1.53 (2H, m) | 25.05 | 1.34 (2H, m) | 25.6 | 1.57 (4H, m) | ||
| 13′ | 26.35 | 1.65 (4H, m) | 25.93 | 1.64 (2H, m) | 36.34 | 1.37 (4H, m) | ||
| 14′ | 40.68 | 3.17 (2H, m) | 40.48 | 3.02 (2H, m) | 40.64 | 3.08 (2H, m) | ||
| 16′ | 157.25 | 157.38 | 157.23 | |||||
| MeO-C3′ | 54.74 | 3.71 (3H, s) | 70.35 | 3.73 (6H, s) | 55.53 | 3.85 (6H, s) | ||
| MeO-C5′ | 70.35 | 3.73 (6H, s) | 55.53 | 3.85 (6H, s) | ||||
a
Prime positions are identical to the non-prime positions since the compound is symmetrical.
b
s: singlet, d: doublet, t: triplet; dd: doublet of doublets, dt: doublet of triplets, and m: multiplet.
c
These peaks overlap; therefore, the number of protons is the total number for both positions.
d
Overlap with solvent peak; n.d. not defined.