Ure was stirred for 7 h at room temperature, after which the solvent was evaporated. The residue was extracted many times with ether, filtered, and concentrated. The residue was purified by column chromatography (SiO2, hexanes H2Cl2 = 10:1) to afford 6 (138 mg, +67 (c 0.74, acetone); 1H NMR (CDCl3, 69 ) as a colorless strong. Mp 823.five , 300 MHz) 7.46.30 (m, 5H), 7.20 (d, J = 8.4 Hz, 1H), 6.78 (br d, J = eight.four Hz, 1H), 6.74 (br s, 1H), five.35 (br s, 1H), five.04 (s, 2H), 2.94.84 (m, 2H), 2.40.08 (m, 4H), 2.00.87 (m, 3H), 1.65.28 (m, 7H), 1.09 (d, J = six.six Hz, 3H), 0.89 (t, J = 7.3 Hz, 3H), 0.83 (s, 3H); 13C NMR (CDCl3, 75 MHz) 160.two, 155.9, 137.six, 136.7, 132.9, 128.0, 127.three, 127.0, 125.six, 120.4, 114.four, 111.8, 70.0, 56.4, 47.eight, 44.7, 37.eight, 35.four, 33.six, 31.3, 30.3, 30.2, 28.2, 27.0, 21.three, 17.1, 12.four. Anal. Calcd for C29H36O: C, 86.95; H, 9.06. Identified: C, 86.99; H, 9.12. 4.2.four. (20S) 3-Hydroxy-19,24-dinorchola-1,3,5(10),16-tetraene (7)–Cleavage in the benzyl ether 6 (73 mg, 0.18 mmol) with sodium metal in n-butanol was carried out inside a fashion similar towards the cleavage of 8. Purification in the residue by column chromatography (SiO2, hexanes thyl acetate gradient = five:1) gave unreacted beginning material (17 mg) followed by 7 (46 mg, 81 ) as a colorless solid. Mp 925 , +86.three (c 0.32, 1H NMR (acetone-d ) 7.05 (d, J = eight.four Hz, 1H), six.56 (dd, J = 2.1, 8.four Hz, 1H), acetone); six six.51 (d, J = 2.1 Hz, 1H), 5.35 (br s, 1H), 2.82.73 (m, 2H), two.37.28 (m, 1H), 2.22.05 (m, 2H), 1.97.85 (m, 4H), 1.60.26 (m, 8H), 1.07 (d, J = 7.2 Hz, 3H), 0.87 (t, J = 7.five Hz, 3H), 0.82 (s, 3H); 13C NMR (acetone-d6) 162.5, 156.7, 139.3, 133.2, 127.7, 122.7, 117.1, 114.7, 58.eight, 50.0, 47.1, 40.4, 37.7, 35.eight, 33.4, 32.five, 32.two, 30.six, 29.3, 23.two, 19.0, 14.1. Anal. Calcd for C22H30O/6H2O: C, 84.28; H, 9.75. Located: C, 84.28; H, 9.82.Bioorg Med Chem. Author manuscript; out there in PMC 2015 January 01.McCullough et al.Page4.2.five. (20S) 3-Hydroxy-19,24-Dinorchola-1,3,5(10),16-tetraen-23-ol (11)–To a remedy of 8 (394 mg, 0.947 mmol) in n-butanol (20 mL), at 70 , was added sodium metal (0.87 g, 38 mmol) in modest pieces. Right after all the sodium had reacted, the reaction mixture was cooled to room temperature and quenched with water, followed by saturated aqueous NH4Cl.Fludarabine phosphate The reaction mixture was extracted a number of times with ether, the combined extracts had been dried (MgSO4) and concentrated.Cibinetide The residue was purified by column chromatography (SiO2, hexanes thyl acetate gradient = four:1 to 2:1) to afford unreacted beginning material (91 +77.PMID:23659187 5 (c mg) followed by 11 (150 mg, 49 ) as a colorless strong. Mp 174.576 , 1.50, acetone); 1H NMR (acetone-d6) 8.15 (s, phenol OH), 7.04 (d, J = eight.4 Hz, 1H), 6.56 (dd, J = two.7, 8.4 Hz, 1H), six.51 (d, J = two.7 Hz, 1H), 5.38 (br s, 1H), three.64.52 (m, 3H), two.842.74 (m, 2H), two.42.28 (m, 2H), two.20.08 (m, 1H), 1.96.70 (m, 4H), 1.60.30 (m, 7H), 1.ten (d, J = 7.2 Hz, 3H), 0.82 (s, 3H); 13C NMR (acetone-d6) 162.eight, 156.six, 139.two, 133.0, 127.six, 122.six, 117.0, 114.six, 61.four, 58.7, 49.9, 47.0, 43.0, 40.3, 37.5, 33.2, 32.0, 30.9, 30.five, 29.two, 23.7, 19.0. Anal. Calcd for C22H30O2: C, 80.94; H, 9.26. Found: C, 80.67; H, 9.32. 4.two.6. 17,23-Epoxy-3-(phenylmethoxy)-19,24-dinorchola-1,three,5(10)-triene (9)–To a remedy of 8 (56 mg, 0.14 mmol) in CHCl3 (2 mL) was added a drop of concentrated HCl. The mixture was allowed to stand stirred for 24 h at room temperature, and then passed by means of a short column of silica gel employing hexanes thyl acetate as eluent. Concentration of the eluent gave 9 (50.
