Heterocyclic Analogues of Xanthone and Xanthione. 1H-Pyrano[2,3-c:6,5-c]dipyrazol-4(7H)-ones and Thiones: Synthesis and NMR Data
Abstract
:1. Introduction
2. Results and Discussion
2.1. Chemistry
2.2. NMR Spectroscopic Investigations
3. Experimental
3.1. General
3.2. Synthetic procedures
3.2.1. General procedure for the synthesis of the carbaldehydes 6a and 6b
3.2.2. Preparation of 5-chloro-1-phenyl-1H-pyrazole-4-carboxylic acid (7a)
3.2.3. Preparation of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid (7b)
3.2.4. General procedure for the synthesis of the acid chlorides 2a and 2b
3.2.5. Acylation of Pyrazolones: General procedure for the synthesis of 3a-g and 8a-b
Entry | Structure | Spectroscopic and analytical data |
---|---|---|
3a | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 8.26 (s, 1H, H-3’), 8.02 (s, 1H, H-3), 7.89 (m, 2H, N1-Ph H-2,6), 7.54–7.58 (3H, N1’-Ph H-3,4,5), 7.57 (m, 2H, N1’-Ph H-2,6), 7.50 (m, 2H, N1-Ph H-3,5), 7.35 (m, 1H, N1-Ph H-4), 6.0–8.5 (very broad s, 1H, OH); 13C-NMR (75 MHz, CDCl3): δ (ppm) 181.5 (C=O), 159.9 (C-5, 3J(C-5,H-3) = 4.9 Hz), 141.1 (C-3’, 1J(C-3’,H-3’) = 190.7 Hz), 138.5 (C-3, 1J(C-3,H-3) = 189.3 Hz), 137.2 (N1-Ph C-1 and N-1’-Ph C-1), 130.5 (C-5’, 3J(C-5’,H-3’) = 5.9 Hz), 129.5 (N1’-Ph C-4), 129.3 (N1’-Ph C-3,5), 129.2 (N1-Ph C-3,5), 127.2 (N1-Ph C-4), 125.5 (N1’-Ph C-2,6), 121.1 (N1-Ph C-2,6), 117.9 (C-4’, 2J(C-4’,H-3’) = 10.3 Hz), 103.7 (C-4, 2J(C-4,H-3) = 11.1 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −185.2 (N-1), −159.9 (N-1’), −97.9 (N-2), −72.4 (N-2’); IR: 1656 (C=O) cm-1; MS m/z (%): 364/266 (M+, 23/8), 329 (38), 186 (100), 91 (18), 77 (52), 51 (22). Calcd. for C19H13ClN4O2 (364.79): C, 62.56; H, 3.59; N, 15.36. Found: C, 62.39; H, 3.50; N, 15.16. |
3b | | 1H-NMR (500 MHz, CDCl3): δ (ppm) 10.18 (broad s, 1H, OH), 7.92 (s, 1H, H-3), 7.89 (m, 2H, N1-Ph H-2,6), 7.58 (m, 2H, N1’-Ph H-2,6), 7.53 (m, 2H, N1’-Ph H-3,5), 7.49 (m, 2H, N1-Ph H-3,5), 7.48 (1H, N1’-Ph H-4), 7.34 (m, 1H, N1-Ph H-4), 2.50 (s, 3H, 3’-Me); 13C-NMR (125 MHz, CDCl3): δ (ppm) 183.0 (C=O), 160.0 (C-5, 3J(C-5,H-3) = 4.7 Hz), 150.5 (C-3’, 2J(C-3’,3’-Me) = 6.9 Hz), 140.1 (C-3, 1J(C-3,H-3) = 191.1 Hz), 137.3 (N1’-Ph C-1), 137.2 (N1-Ph C-1), 129.2 (N1’-Ph C-3,5), 129.15 (N1-Ph C-3,5), 129.05 (N1’-Ph C-4), 127.6 (C-5’), 127.0 (N1-Ph C-4), 125.4 (N1’-Ph C-2,6), 120.9 (N1-Ph C-2,6), 117.4 (C-4’, 3J(C-4’,3’-Me) = 2.8 Hz), 104.2 (C-4, 2J(C-4,H-3) = 10.6 Hz), 13.8 (3’-Me, 1J = 129.1 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −186.0 (N-1), −167.8 (N-1’), −97.3 (N-2), −75.8 (N-2’); IR: 1559 (C=O) cm-1; MS m/z (%): 378/380 (M+, 12/4), 343 (45), 219 (11), 186 (100), 118 (12), 91 (15), 77 (43), 51 (16). Calcd. for C20H15ClN4O2 (378.81): C, 63.41; H, 3.99; N, 14.79. Found: C, 63.24; H, 3.81; N, 14.74. |
3c | | 1H-NMR (500 MHz, CDCl3): δ (ppm) 8.01 (s, 1H, H-3’), 7.87 (m, 2H, N1-Ph H-2,6), 7.60 (m, 2H, N1’-Ph H-2,6), 7.55 (m, 2H, N1’-Ph H-3,5), 7.52 (m, 1H, N1’-Ph H-4), 7.48 (m, 2H, N1-Ph H-3,5), 7.32 (m, N1-Ph H-4), 2.39 (s, 3H, 3-Me), OH not found; 13C-NMR (125 MHz, CDCl3): δ (ppm) 182.9 (C=O), 161.0 (C-5), 147.3 (C-3, 2J(C-3,3-Me) = 6.8 Hz), 140.8 (C-3’, 1J(C-3’,H-3’) = 192.0 Hz), 137.3 (N1’-Ph C-1), 137.1 (N1-Ph C-1), 129.3 (N1’-Ph C-3,4,5), 129.1 (N1-Ph C-3,5), 129.0 (C-5’, 3J(C-5’,H-3’) = 5.6 Hz), 126.9 (N1-Ph C-4), 125.4 (N1’-Ph C-2,6), 120.9 (N1-Ph C-2,6), 118.4 (C-4’, 2J(C-4’,H-3’) = 10.1 Hz), 104.4 (C-4, 3J(C-4,3-Me) = 2.7 Hz), 15.6 (3-Me, 1J = 128.8 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −190.3 (N-1), −161.7 (N-1’), −100.8 (N-2), −74.2 (N-2’); IR: 1619 (C=O) cm-1; MS m/z (%): 378/380 (M+, 8/3), 342 (48), 200 (100), 91 (37), 77 (58), 51 (25). Calcd. for C20H15ClN4O2 (378.81): C, 63.41; H, 3.99; N, 14.79. Found: C, 63.71; H, 3.91; N, 14.69. |
3d | | 1H-NMR (500 MHz, CDCl3): δ (ppm) 9.20 (broad s, 1H, OH), 7.87 (m, 2H, N1-Ph H-2,6), 7.56 (m, 2H, N1’-Ph H-2,6), 7.52 (m, 2H, N1’-Ph H-3,5), 7.47 (m, 2H, N1-Ph H-3,5), 7.47 (m, 1H, N1’-Ph H-4), 7.31 (m, 1H, N1-Ph H-4), 2.41 (s, 3H, 3’-Me), 2.23 (s, 3H, 3-Me); 13C-NMR (125 MHz, CDCl3): δ (ppm) 183.8 (C=O), 160.8 (C-5), 148.8 (C-3’, 2J(C-3’,3’-Me) = 6.8 Hz), 148.1 (C-3, 2J(C-3,3-Me) = 6.7 Hz), 137.4 (N1’-Ph C-1), 137.1 (N1-Ph C-1), 129.2 (N1’-Ph C-3,5), 129.1 (N1-Ph C-3,5), 128.9 (N1’-Ph C-4), 126.8 (N1-Ph C-4), 126.7 (C-5’), 125.2 (N1’-Ph C-2,6), 120.7 (N1-Ph C-2,6), 117.8 (C-4’, 3J(C-4’,3’-Me) = 3.0 Hz), 105.5 (C-4, 3J(C-4,3-Me) = 2.8 Hz), 13.9 (3-Me, 1J = 129.0 Hz), 13.0 (3’-Me, 1J = 128.9 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −190.3 (N-1), −168.8 (N-1’), −100.0 (N-2), −76.6 (N-2’); MS m/z (%): 392/394 (M+, 5/2), 356 (39), 219 (10), 200 (100), 132 (13), 91 (31), 77 (40), 67 (12), 51 (15). Calcd. for C21H17ClN4O2 (392.84): C, 64.21; H, 4.36; N, 14.26. Found: C, 64.04; H, 4.18; N, 14.21. |
3e | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 10.35 (broad s, 1H, OH), 7.94 (s, 1H, H-3’), 7.44–7.59 (m, 5H, N1’-Ph), 3.62 (s, 3H, N1-Me), 2.27 (s, 3H, 3-Me); 13C-NMR (75 MHz, CDCl3): δ (ppm) 183.4 (C=O), 160.2 (C-5, 3J(C-5,N1-Me) = 2.3 Hz), 146.2 (C-3, 2J(C-3,3-Me) = 6.9 Hz), 140.6 (C-3’, 1J(C-3’,H-3’) = 191.7 Hz), 137.4 (N1’-Ph C-1), 129.2 (N1’-Ph C-3,4,5), 128.6 (C-5’, 3J(C-5’,H-3’) = 5.7 Hz), 125.3 (N1’-Ph C-2,6), 119.0 (C-4’, 2J(C-4’,H-3’) = 10.1 Hz), 103.2 (C-4, 3J(C-4,3-Me) = 2.7 Hz), 32.5 (N1-Me, 1J = 140.9 Hz), 15.2 (3-Me, 1J = 128.6 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −207.9 (N-1), −162.2 (N-1’), −100.5 (N-2), −74.7 (N-2’); IR: 1636 (C=O) cm-1;MS m/z (%): 316/318 (M+, 11/4), 281 (26), 138 (100), 77 (21), 51 (17). Calcd. for C15H13ClN4O2 (316.74): C, 56.88; H, 4.14; N, 17.69. Found: C, 57.12; H, 3.97; N, 17.61. |
3f | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 8.18 (s, 1H, H-3’), 7.30–8.00 (very broad s, 1H, OH), 7.82 (broad, s, 1H, H-3), 7.55 (m, 2H, N1’-Ph H-2,6), 7.52 (m, 3H, N1’-Ph H-3,4,5), 7.31 (m, 2H, CH2-Ph H-2,6), 6.88 (CH2-Ph H-3,-5), 5.13 (broad s, 2H, CH2), 3.79 (s, 3H, OMe); 13C-NMR (75 MHz, CDCl3): δ (ppm) 181.7 (C=O), 159.5 (CH2-Ph C-4), 159.0 (C-5), 141.1 (C-3’, 1J(C-3’,H-3’) = 190.7 Hz), 137.9 (C-3, 1J(C-3,H-3) = 188.8 Hz), 137.3 (N1’-Ph C-1), 130.3 (C-5’), 129.6 (CH2-Ph C-2,6), 129.4 (N1’-Ph C-4), 129.2 (N1’-Ph C-3,5), 127.5 (CH2-Ph C-1), 125.5 (N1’-Ph C-2,-6), 118.2 (C-4’, 2J(C-4’,H-3’) = 10.0 Hz), 114.2 (CH2-Ph C3,5), 103.1 (C-4), 55.3 (OMe, 1J = 143.9 Hz), 49.8 (CH2, 1J = 140.6 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −189.2 (N-1), −160.3 (N-1’), −98.3 (N-2), −73.1 (N-2’); IR: 1621 (C=O) cm-1;MS m/z (%): 408/410 (M+, 7/2), 373 (25), 121 (100), 77 (23). Calcd. for C21H17ClN4O3 (408.84): C, 61.69; H, 4.19; N, 13.70. Found: C, 61.47; H, 4.13, N, 13.55. |
3g | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.70–8.20 (broad s, 1H, OH), 7.96 (s, 1H, H-3’), 7.58 (m, 2H, N1’-Ph H-2,6), 7.53 (m, 2H, N1’-Ph H-3,5), 7.48 (m, 1H, N1’-Ph H-4), 7.28–7.38 (m, 5H, CH2-Ph), 5.12 (s, 2H, CH2), 2.28 (s, 3H, 3-Me); 13C-NMR (75 MHz, CDCl3): δ (ppm) 183.3 (C=O), 160.3 (C-5, 3J(C-5,CH2) = 2.4 Hz), 146.6 (C-3, 2J(C-3,3-Me) = 7.0 Hz), 140.7 (C-3’, 1J(C-3’,H-3’) = 192.0 Hz), 137.4 (N1’-Ph C-1), 135.5 (CH2-Ph C-1), 129.2 (N1’-Ph C-3,4,5), 128.7 (CH2-Ph C-3,5 and C-5’, 3J(C-5’,H-3’) = 5.7 Hz), 128.0 (CH2-Ph C-2,4,6), 125.3 (N1’-Ph C-2,6), 118.9 (C-4’, 2J(C-4’,H-3’) = 10.1 Hz), 103.4 (C-4, 3J(C-4,3-Me) = 2.6 Hz), 49.8 (CH2, 1J = 140.2 Hz), 15.4 (3-Me, 1J = 128.6 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −196.4 (N-1), −162.1 (N-1’), −101.1 (N-2), −74.7 (N-2’); IR: 1633 (C=O) cm-1; MS m/z (%): 392/394 (M+, 8/3), 356 (91), 91 (100), 77 (25), 51 (18). Calcd. for C21H17ClN4O2 (392.84): C, 64.21; H, 4.36; N, 14.26. Found: C, 64.13; H, 4.27; N, 14.11. |
8a | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.52 (m, 5H, Ph-H), 6.04 (s, 1H, H-4), 3.74 (s, 3H, N-Me), 2.59 (s, 3H, 3’-Me), 2.25 (s, 3H, 3-Me); 13C-NMR (75Hz, CDCl3): δ (ppm) 157.3 (C=O), 153.1 (C-3’, 2J(C-3’,3’-Me) = 6.9 Hz), 147.2 (C-3, 2J(C-3,3-Me) = 6.7 Hz, 2J(C-3,H-4) = 4.3 Hz), 144.6 (C-5, 3J(C-5,N-CH3) = 2.2 Hz, 2J(C 5,H-4) = 4.4 Hz), 137.2 (Ph-C-1), 132.2 (C-5’), 129.3 (Ph-C-4), 129.2 (Ph-C-3,5), 125.5 (Ph-C-2,-6), 108.3 (C-4’, 3J(C-4’,3’-Me) = 2.7 Hz), 93.9 (C-4, 1J(C-4,H-4) = 181.2 Hz, 3J(C-4,3-Me) = 3.5 Hz), 14.8 (3’-Me, 1J = 129.5Hz), 14.2 (3-Me, 1J = 127.5 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −202.2 (N-1), −165.8 (N-1’), −98.9 (N-2), −75.7 (N-2’); IR: 1745 (C=O) cm-1; MS m/z (%): 330 (M+, 0.1), 219 (100), 77 (42), 51 (19). Calcd. for C16H15ClN4O2 (330.77): C, 58.10; H, 4.57; N, 16.94. Found: C, 58.14; H, 4.37; N, 16.90. |
8b | | 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.53 (d, 1H, H-3, 3J(H3,H4) = 2.1 Hz), 7.52 (m, 5H, N1’-Ph), 7.12 (m, 2H, CH2-Ph H-2,6), 6.82 (m, 2H, CH2-Ph H-3,5), 6.30 (d, 1H, H-4, 3J(H4,H3) = 2.1 Hz), 5.28 (s, 2H, CH2), 3.75 (s, 3H, O-Me), 2.52 (s, 3H, 3’-Me); 13C-NMR (75 MHz, CDCl3): δ (ppm) 159.2 (CH2-Ph C4), 157.2 (C=O), 153.2 (C-3’, 2J(C-3’,3’-Me) = 7.0 Hz), 144.3 (C-5), 138.7 (C-3, 1J(C-3,H-3) = 187.6 Hz, 2J(C-3,H-4) = 4.8 Hz), 137.2 (N1’-Ph C-1), 132.2 (C-5’), 129.4 (N1’-Ph C-4), 129.2 (N1’-Ph C-3,5), 128.4 (CH2-Ph C-2,6), 128.3 (CH2-Ph C-1), 125.5 (N1’-Ph C-2,6), 114.1 (CH2-Ph C-3,5), 108.2 (C-4’, 3J(C-4’,3’-Me) = 2.7 Hz), 94.9 (C-4, 1J(C-4,H-4) = 183.4 Hz, 2J(C-4,H-5) = 10.5 Hz), 55.2 (O-Me, 1J = 143.8 Hz), 51.3 (CH2, 1J = 140.0 Hz, 3J(CH2,Ph-H-2,6) = 4.3 Hz), 14.8 (3’-Me, 1J = 129.6 Hz); 15N-NMR (50 MHz, CDCl3): δ (ppm) −185.1 (N-1), −165.7 (N-1’), −95.3 (N-2), −75.7 (N-2’); IR: 1745 (C=O) cm-1; MS m/z (%): 422 (M+, 0.1), 219 (100), 121 (25), 77 (20). Calcd. for C22H19ClN4O3 (422.86): C, 62.49; H, 4.53; N, 13.25. Found: C, 62.45; H, 4.40; N, 13.15. |
3.2.6. Cyclization of 4-Aroylpyrazolones 3a-g: General procedure for the synthesis of 4a-b, 4d-g
3.2.7. General procedure for the synthesis of 5a-b and 5d-g
3.2.8. General procedure for the synthesis of 4x and 5x
Comp | Solvent | H of R1 | H of R3 | H of R5 | H of R7 |
---|---|---|---|---|---|
4a | CDCl3 | Ph: 7.82 (2,6), 7.55 (3,5), 7.44 (4) | 8.22 (H-3) | 8.22 (H-5) | Ph: 7.82 (2,6), 7.55 (3,5), 7.44 (4) |
4b | CDCl3 | Ph: 7.78 (2,6), 7.52 (3,5), 7.40 (4) | 2.66 (Me) | 8.17 (H-5) | Ph: 7.80 (2,6), 7.53 (3,5), 7.43 (4) |
4d | CDCl3 | Ph: 7.78 (2,6), 7.51 (3,5), 7.39 (4) | 2.65 (Me) | 2.65 (Me) | Ph: 7.78 (2,6), 7.51 (3,5), 7.39 (4) |
4e | CDCl3 | 3.87 (Me) | 2.55 (Me) | 8.13 (H-5) | Ph: 7.79 (2,6), 7.56 (3,5), 7.43 (4) |
4f | CDCl3 | Ph: 7.28 (2,6), 6.89 (3,5); 5.37 (CH2), 3.79 (OMe) | 8.05 (H-3) | 8.17 (H-5) | Ph: 7.66 (2,6), 7.56 (3,5), 7.46 (4) |
4g | CDCl3 | Ph: 7.37 (4), 7.36 (3,5), 7.31 (2,6); 5.35 (CH2) | 2.60 (Me) | 8.12 (H-5) | Ph: 7.60 (2,6), 7.52 (3,5), 7.42 (4) |
5a | CDCl3 | Ph: 7.84 (2,6), 7.57 (3,5), 7.46 (4) | 8.39 (H-3) | 8.39 (H-5) | Ph: 7.84 (2,6), 7.57 (3,5), 7.46 (4) |
5b | CDCl3 | Ph: 7.81 (2,6), 7.54 (3,5), 7.42 (4) | 2.78 (Me) | 8.32 (H-5) | Ph: 7.82 (2,6), 7.55 (3,5), 7.44 (4) |
5d | CDCl3 | Ph: 7.80 (2,6), 7.53 (3,5), 7.41 (4) | 2.80 (Me) | 2.80 (Me) | Ph: 7.80 (2,6), 7.53 (3,5), 7.41 (4) |
5e | CDCl3 | 3.89 (Me) | 2.65 (Me) | 8.27 (H-5) | Ph: 7.81 (2,6), 7.57 (3,5), 7.45 (4) |
5f | CDCl3 | Ph: 7.28 (2,6), 6.90 (3,5); 5.38 (CH2), 3.79 (OMe) | 8.20 (H-3) | 8.32 (H-5) | Ph: 7.66 (2,6), 7.56 (3,5), 7.47 (4) |
5g | CDCl3 | Ph: 7.38 (3,4,5), 7.33 (2,6); 5.37 (CH2) | 2.73 (Me) | 8.29 (H-5) | Ph: 7.61 (2,6), 7.53 (3,5), 7.43 (4) |
4x | DMSO- d6 | Ph: 7.85 (2,6), 7.62 (3,5), 7.48 (4) | 8.24 (H-3) | 8.56 (H-5) | 13.78 (NH) |
5x | DMSO- d6 | Ph: 7.87 (2,6), 7.64 (3,5), 7.50 (4) | 8.34 (H-3) | 8.66 (H-5) | 14.00 (NH) |
Comp | C-3 | C-3a | C-4 | C-4a | C-5 | C-7a | C-8a | C of R1 | C of R3 | C of R5 | C of R7 |
---|---|---|---|---|---|---|---|---|---|---|---|
4a | 136.7 | 108.8 | 169.7 | 108.8 | 136.7 | 151.3 | 151.3 | Ph: 136.6 (1), 129.6 (3,5), 128.3 (4), 121.3 (2,6) | - | - | Ph: 136.6 (1), 129.6 (3,5), 128.3 (4), 121.3 (2,6) |
4b | 148.1 | 106.5 | 170.6 | 108.9 | 136.6 | 151.3 | 151.4 | Ph: 136.6 (1), 129.48 (3,5), 127.8 (4), 121.1 (2,6) | 14.0 (Me) | - | Ph: 136.7 (1), 129.53 (3,5), 128.1 (4), 121.2 (2,6) |
4d | 148.0 | 106.6 | 171.8 | 106.6 | 148.0 | 151.5 | 151.5 | Ph: 136.7 (1), 129.5 (3,5), 127.7 (4), 121.0 (2,6) | 14.0 (Me) | 14.0 (Me) | Ph: 136.7 (1), 129.5 (3,5), 127.7 (4), 121.0 (2,6) |
4e | 146.8 | 105.0 | 170.7 | 108.7 | 136.6 | 151.3 | 152.6 | 34.1 (Me) | 13.9 (Me) | - | Ph: 136.7 (1), 129.6 (3,5), 128.1 (4), 121.5 (2,6) |
4f | 135.5 | 107.8 | 169.8 | 108.6 | 136.7 | 151.4 | 152.0 | Ph: 159.9 (4), 129.4 (2,6), 126.2 (1), 114.4 (3,5); 55.3 (OMe), 52.4 (CH2) | - | - | Ph: 136.6 (1), 129.6 (3,5), 128.2 (4), 121.6 (2,6) |
4g | 146.9 | 105.5 | 170.7 | 108.8 | 136.6 | 151.3 | 152.4 | Ph: 134.6 (1), 129.0 (3,5), 128.6 (4), 127.7 (2,6); 52.3 (CH2) | 14.0 (Me) | - | Ph: 136.7 (1), 129.5 (3,5), 128.0 (4), 121.4 (2,6) |
5a | 138.1 | 117.8 | 192.1 | 117.8 | 138.1 | 145.5 | 145.5 | Ph: 136.6 (1), 129.7 (3,5), 128.3 (4), 121.3 (2,6) | - | - | Ph: 136.6 (1), 129.7 (3,5), 128.3 (4), 121.3 (2,6) |
5b | 150.1 | 114.8 | 193.5 | 118.1 | 138.2 | 145.1 | 146.0 | Ph: 136.4 (1), 129.56 (3,5), 128.0 (4), 121.2 (2,6) | 15.6 (Me) | - | Ph: 136.6 (1), 129.6 (3,5), 128.2 (4), 121.1 (2,6) |
5d | 150.2 | 115.1 | 195.5 | 115.1 | 150.2 | 145.8 | 145.8 | Ph: 136.5 (1), 129.6 (3,5), 127.9 (4), 121.2 (2,6) | 15.9 (Me) | 15.9 (Me) | Ph: 136.5 (1), 129.6 (3,5), 127.9 (4), 121.2 (2,6) |
5e | 148.8 | 113.5 | 193.5 | 117.7 | 138.1 | 145.3 | 147.3 | 34.2 (Me) | 15.2 (Me) | - | Ph: 136.7 (1), 129.6 (3,5), 128.2 (4), 121.4 (2,6) |
5f | 136.9 | 117.0 | 192.2 | 117.5 | 138.1 | 145.5 | 146.2 | Ph: 159.9 (4), 129.4 (2,6), 126.0 (1), 114.4 (3,5); 55.3 (OMe), 52.5 (CH2) | - | - | Ph: 136.5 (1), 129.6 (3,5), 128.3 (4), 121.5 (2,6) |
5g | 148.9 | 114.1 | 193.6 | 117.9 | 138.2 | 145.2 | 147.0 | Ph: 134.4 (1), 129.1 (3,5), 128.7 (4), 127.8 (2,6); 52.4 (CH2) | 15.4 (Me) | - | Ph: 136.6 (1), 129.6 (3,5), 128.1 (4), 121.3 (2,6) |
4x | 136.3 | 107.4 | 170.5 | 106.7 | 128.6 | 160.6 | 153.0 | Ph: 136.5 (1), 129.6 (3,5), 128.0 (4), 121.8 (2,6) | - | - | - |
5x | 137.7 | 116.9 | 193.5 | 115.8 | 130.2 | 155.0 | 147.6 | Ph: 136.3 (1), 129.6 (3,5), 128.2 (4), 121.8 (2,6) | - | - | - |
Comp | J of C-3 | J of C-3a | J of C-4a | J of C-5 | J of C-7a | J of C-8a | other couplings |
---|---|---|---|---|---|---|---|
4a | 1J = 194.7 | 2J(H-3) = 9.9 | 2J(H-5) = 9.9 | 1J = 194.7 | 3J(H-5) = 5.2 | 3J(H-3) = 5.2 | |
4b | 2J(3-Me) = 7.2 | 3J(3-Me) = 2.9 | 2J(H-5) = 10.0 | 1J = 194.4 | 3J(H-5) = 5.1 | 1J(3-Me) = 129.4 | |
4d | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.7 | 3J(5-Me) = 2.7 | 2J(5-Me) = 7.1 | 1J(3-Me) = 129.3, 1J(5-Me) = 129.3 | ||
4e | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.6 | 2J(H-5) = 9.9 | 1J = 194.1 | 3J(H-5) = 5.2 | 3J(N-Me) = 2.1 | 1J(N-Me) = 141.7, 1J(3-Me) = 129.1 |
4f | 1J = 194.1 | 2J(H-3) = 10.0 | 2J(H-5) = 9.9 | 1J = 194.6 | 3J(H-5) = 5.2 | 3J(H-3) ~ 5.2, 3J(N-CH2) = 2.8 | 1J(OMe) = 144.1, 1J(N-CH2) = 141.5, 3J(NCH2,Ph H-2,6) = 4.9, 2J(Ph C-1,NCH2) = 4.7, 3J(Ph C-2/6,NCH2) = 4.4 |
4g | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.8 | 2J(H-5) = 10.0 | 1J = 194.2 | 3J(H-5) = 5.2 | 3J(N-CH2) = 2.7 | 1J(N-CH2) = 141.0, 1J(3-Me) = 129.2, 3J(NCH2,Ph H-2,6) = 4.7 |
5a | 1J = 195.8 | 2J(H-3) = 9.3 | 2J(H-5) = 9.3 | 1J = 195.8 | 3J(H-5) = 5.1 | 3J(H-3) = 5.1 | |
5b | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.6 | 2J(H-5) = 9.1 | 1J = 195.5 | 3J(H-5) = 5.0 | 1J(3-Me) = 129.7 | |
5d | 2J(3-Me) = 7.2 | 3J(3-Me) = 2.5 | 3J(5-Me) = 2.5 | 2J(5-Me) = 7.2 | 1J(3-Me) = 129.6, 1J(5-Me) = 129.6 | ||
5e | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.7 | 2J(H-5) = 9.1 | 1J = 195.3 | 3J(H-5) = 5.1 | 3J(N-Me) = 2.4 | 1J(N-Me) = 141.9, 1J(3-Me) = 129.4 |
5f | 1J = 195.0 | 2J(H-3) = 9.4 | 2J(H-5) = 9.3 | 1J = 195.5 | 3J(H-5) = 5.1 | 3J(H-3) = 5.1, 3J(N-CH2) = 2.6 | 1J(OMe) = 144.1, 1J(N-CH2) = 141.4, 3J(NCH2,Ph H-2,6) = 4.6 |
5g | 2J(3-Me) = 7.1 | 3J(3-Me) = 2.7 | 2J(H-5) = 9.2 | 1J = 195.3 | 3J(H-5) = 5.1 | 3J(N-CH2) = 2.8 | 1J(N-CH2) = 141.2, 1J(3-Me) = 129.5, 3J(NCH2, Ph H-2,6) = 4.4 |
4x | 1J = 193.8 | 2J(H-3) = 10.2 | 2J(H-5) ~ 8.5 | 1J ~ 195.0 | 3J(H-5) =not resolved | 3J(H-3) = 5.2 | |
5x | 1J = 194.7 | 2J(H-3) = 9.5 | 2J(H-5) = 7.8 | 1J = 195.9 | 3J(H-5) = 8.5 | 3J(H-3) = 4.9 |
Comp | N-1 | N-2 | N-6 | N-7 |
---|---|---|---|---|
4a | −186.8 | −86.8 | −86.8 | −186.8 |
4b | −193.1 | −93.6 | −87.7 | −187.1 |
4d | −193.4 | −94.2 | −94.2 | −193.4 |
4e | −211.8 | −91.7 | −88.0 | −187.5 |
4f | −191.8 | −85.2 | −87.5 | −187.3 |
4g | −200.0 | −91.3 | −88.2 | −187.4 |
5a | −187.6 | −84.5 | −84.5 | −187.6 |
5b | −195.3 | −92.1 | −85.5 | −188.0 |
5d | −196.2 | −92.9 | −92.9 | −196.2 |
5e | −213.7 | −89.7 | −85.6 | −188.2 |
5f | −192.4 | −82.2 | −84.9 | −187.9 |
5g | −201.9 | −89.5 | −85.8 | −188.2 |
4x | −186.4 | −87.7 | −179.2* | −179.2* |
5x | −186.7 | −84.3 | −175.5* | −175.5* |
3.2.9. General procedure for the synthesis of 9a and 9b
4. Conclusions
Acknowledgements
References and Notes
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Datterl, B.; Tröstner, N.; Kucharski, D.; Holzer, W. Heterocyclic Analogues of Xanthone and Xanthione. 1H-Pyrano[2,3-c:6,5-c]dipyrazol-4(7H)-ones and Thiones: Synthesis and NMR Data. Molecules 2010, 15, 6106-6126. https://doi.org/10.3390/molecules15096106
Datterl B, Tröstner N, Kucharski D, Holzer W. Heterocyclic Analogues of Xanthone and Xanthione. 1H-Pyrano[2,3-c:6,5-c]dipyrazol-4(7H)-ones and Thiones: Synthesis and NMR Data. Molecules. 2010; 15(9):6106-6126. https://doi.org/10.3390/molecules15096106
Chicago/Turabian StyleDatterl, Barbara, Nicole Tröstner, Dorota Kucharski, and Wolfgang Holzer. 2010. "Heterocyclic Analogues of Xanthone and Xanthione. 1H-Pyrano[2,3-c:6,5-c]dipyrazol-4(7H)-ones and Thiones: Synthesis and NMR Data" Molecules 15, no. 9: 6106-6126. https://doi.org/10.3390/molecules15096106