With the rapid development and complex challenges of chemical substances, new drug synthesis pathways are usually the most effective.17261-28-8,2-(Diphenylphosphino)benzoic acid,as a common compound, the synthetic route is as follows.
To a solution of 2-diphenylphosphinobenzoic acid (67 mg, 0.22 mmol) in dry CH2Cl2 (5 mL) under an argon atmosphere N-[3-(dimethylamino)propyl]-N-ethylcarbodiimide (50 mg, 0.26 mmol), hydroxybenzotriazole (36 mg, 0.26 mmol), and (1R,5S)-(-)-cytisine (50 mg, 0.26 mmol) were added at room temperature. The mixture was stirred at room temperature for 24 h and then was directly subjected to flash column chromatography (silica gel, CH2Cl2/CH3OH = 50:1) to give 104 mg (99percent yield) of 3 as a white solid; m.p. 126-128 ¡ãC. [alpha]D20 = -198.4 (c 0.64, CHCl3). 1H NMR (600 MHz, CDCl3, 253 K): 1:0.9 mixture of rotamers; signals for B-chair conformer: delta = 7.40-7.38 (m, 2H, Har), 7.37-7.34 (m, 1H, 10-H), 7.35-7.33 (m, 2H, Har), 7.32-7.30 (m, 3H, Har), 7.24-7.21 (m, 1H, Har), 7.20-7.16 (m, 3H, Har), 7.10 (dt, JH,H = 7.5, 0.6 Hz, 1H, Har), 7.06-7.02 (m, 1H, Har), 6.61 (dd, JH,H = 9.1, 1.2 Hz, 1H, 9-H), 6.15 (ddd, JH,H = 7.6, 3.6, 0.7 Hz, 1H, Har), 5.88 (dd, JH,H = 6.8, 1.0 Hz, 1H, 11-H), 4.85 (d, JH,H = 12.4 Hz, 1H, 4-Heq), 4.26 (d, JH,H = 15.6 Hz, 1H, 6-H), 3.90 (dd, JH,H = 15.6, 6.4 Hz, 1H, 6-H), 3.32 (d, JH,H = 12.7 Hz, 1H, 2-Heq), 2.94 (d, JH,H = 12.4 Hz, 1H, 4-Hax), 2.87 (brs, 1H, 1-H), 2.76 (dd, JH,H = 12.7, 1.6 Hz, 1H, 2-Hax), 2.61 (brs, 1H, 5-H), 2.05-1.92 (m, 2H, 13-H) ppm; resolved signals for A-chair conformer: delta = 7.45-7.42 (m, 1H, Har), 7.06-7.02 (m, 1H, Har), 7.37-7.34 (m, 1H, 10-H), 6.94 (ddd, JH,H = 7.5, 3.3, 0.6 Hz, 1H, Har), 6.54 (dd, JH,H = 9.0, 1.1 Hz, 1H, 9-H), 6.19 (dd, JH,H = 6.8, 0.7 Hz, 1H, 11-H), 4.75 (d, JH,H = 12.8 Hz, 1H, 2-Heq), 4.11 (d, JH,H = 15.6 Hz, 1H, 6-H), 3.74 (dd, JH,H = 15.6, 6.0 Hz, 1H, 6-H), 3.50 (d, JH,H = 12.6 Hz, 1H, 4-Heq), 3.20 (brs, 1H, 1-H), 3.04 (dd, JH,H = 12.8, 1.9 Hz, 1H, 2-Hax), 2.98 (d, JH,H = 12.6 Hz, 1H, 4-Hax), 2.32 (brs, 1H, 5-H), 2.05-1.92 (m, 2H, 13-H) ppm. 13C NMR (150.9 MHz, CDCl3, 253 K): signals for B-chair conformer: delta = 170.15 (Cq, C=O, amide), 163.19 (Cq, C=O, lactam), 148.16 (CH, 12-C), 141.27 (d, J31P,13C = 33.7 Hz, Cq, Car), 138.61 (CH, 10-C), 135.82 (d, J31P,13C = 9.9 Hz, Cq, Car), 135.70 (d, J31P,13C = 9.4 Hz, Cq, Car), 134.26 (d, J31P,13C = 20.7 Hz, 2 CH, Car), 134.00 (CH, Car), 133.63 (Cq, CCO), 133.06 (d, J31P,13C = 18.8 Hz, 2 CH, Car), 129.96 (CH, Car), 129.09 (CH, Car),129.03 (CH, Car), 128.56 (d, J31P,13C = 6.8 Hz, 2 CH, Car), 128.53 (d, J31P,13C = 7.8 Hz, 2 CH, Car), 128.29 (CH, Car), 126.06 (d, J31P,13C = 7.5 Hz, 1 CH, Car), 117.66 (CH, 9-C), 105.61 (CH, 11-C), 53.13 (d, J31P,13C = 1.8 Hz, CH2, 2-C), 49.01 (CH2, 6-C), 47.22 (CH2, 4-C), 34.37 (CH, 1-C), 26.93 (CH, 5-C), 25.72 (CH2, 13-C) ppm; signals for A-chair conformer: delta = 170.21 (Cq, C=O, amide), 163.26 (Cq, C=O, lactam), 148.18 (CH, 12-C), 141.65 (d, J31P,13C = 33.9 Hz, Cq, Car), 139.50 (CH, 10-C), 135.52 (d, J31P,13C = 8.5 Hz, Cq, Car), 135.42 (d, J31P,13C = 8.9 Hz, Cq, Car), 134.04 (d, J31P,13C = 20.3 Hz, 2 CH, Car), 134.04 (CH, Car), 133.76 (Cq, CCO), 133.03 (d, J31P,13C = 18.8 Hz, 2 CH, Car), 129.96 (CH, Car), 128.87 (CH, Car), 128.55 (CH, Car), 128.49 (CH, Car), 128.31 (d, J31P,13C = 6.5 Hz, 2 CH, Car), 128.27 (d, J31P,13C = 6.3 Hz, 2 CH, Car), 126.23 (d, J31P,13C = 7.9 Hz, 1 CH, Car), 117.19 (CH, 9-C), 106.42 (CH, 11-C), 52.23 (d, J31P,13C = 2.2 Hz, CH2, 4-C), 48.47 (CH2, 6-C), 48.30 (CH2, 2-C), 34.17 (CH, 1-C), 27.26 (CH, 5-C), 25.86 (CH2, 13-C) ppm. 31P{1H} NMR (242.92 MHz, CDCl3, 253 K): signal for B-chair conformer: delta = -14.07 ppm; signal for A-chair conformer: delta = -13.75 ppm. IR (KBr): nu = 3050, 2925, 2854, 1657, 1639, 1580, 1546, 1434, 1424, 1306, 1243, 745, 673 cm-1. MS (ESI): m/z = 479 (100, [M + 1]+), 289 (63). C30H27N2O2P (478.52): calcd. C 75.30, H 5.69, N 5.85, found C 75.63, H 5.81, N 5.96., 17261-28-8
17261-28-8 2-(Diphenylphosphino)benzoic acid 87021, achiral-phosphine-ligands compound, is more and more widely used in various fields.
Reference£º
Article; Philipova, Irena; Stavrakov, Georgi; Vassilev, Nikolay; Nikolova, Rositsa; Shivachev, Boris; Dimitrov, Vladimir; Journal of Organometallic Chemistry; vol. 778; (2015); p. 10 – 20;,
Phosphine ligand
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate