30O3?/2H2O: C, 75.18; H eight.89. Identified: C, 75.36; H, 8.28. four.two.three. (20S) 3-(Phenylmethoxy)-19,24-dinorchola-1,three,five(ten),16-tetraene (six)–To a remedy of five (0.20 g, 0.50 mmol) in benzene (10 mL) in a Schlenk flask was added Rh(PPh3)3Cl (40 mg, 0.043 mmol). The reaction mixture was cooled using a dry ice cetone bath, evacuated beneath higher vacuum, and the program refilled to 1 atm with H2 gas. The mixture was stirred for 7 h at space temperature, then the solvent was evaporated. The residue was extracted various instances with ether, filtered, and concentrated. The residue was purified by column chromatography (SiO2, hexanes H2Cl2 = 10:1) to afford six (138 mg, +67 (c 0.74, acetone); 1H NMR (CDCl3, 69 ) as a colorless strong. Mp 82?3.5 , 300 MHz) 7.46?.30 (m, 5H), 7.20 (d, J = 8.four Hz, 1H), six.78 (br d, J = 8.4 Hz, 1H), six.74 (br s, 1H), 5.35 (br s, 1H), 5.04 (s, 2H), 2.94?.84 (m, 2H), two.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) 160.2, 155.9, 137.6, 136.7, 132.9, 128.0, 127.three, 127.0, 125.6, 120.four, 114.four, 111.8, 70.0, 56.4, 47.8, 44.7, 37.8, 35.4, 33.6, 31.three, 30.3, 30.2, 28.2, 27.0, 21.3, 17.1, 12.four. Anal. Calcd for C29H36O: C, 86.95; H, 9.06. Identified: C, 86.99; H, 9.12. four.2.four. (20S) 3-Hydroxy-19,24-dinorchola-1,3,five(ten),16-tetraene (7)–Cleavage with the benzyl ether 6 (73 mg, 0.18 mmol) with sodium metal in n-butanol was carried out in a fashion similar towards the cleavage of eight. Purification in the residue by column chromatography (SiO2, hexanes thyl acetate gradient = 5:1) gave unreacted beginning material (17 mg) followed by 7 (46 mg, 81 ) as a colorless solid.852913-25-8 In stock Mp 92?5 , +86.6-Bromo-4-chloro-1H-indole Chemical name 3 (c 0.PMID:33608982 32, 1H NMR (acetone-d ) 7.05 (d, J = eight.four Hz, 1H), 6.56 (dd, J = two.1, eight.4 Hz, 1H), acetone); six 6.51 (d, J = 2.1 Hz, 1H), 5.35 (br s, 1H), two.82?.73 (m, 2H), 2.37?.28 (m, 1H), two.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 = 7.5 Hz, 3H), 0.82 (s, 3H); 13C NMR (acetone-d6) 162.five, 156.7, 139.3, 133.two, 127.7, 122.7, 117.1, 114.7, 58.eight, 50.0, 47.1, 40.four, 37.7, 35.eight, 33.4, 32.5, 32.two, 30.6, 29.three, 23.2, 19.0, 14.1. Anal. Calcd for C22H30O?/6H2O: C, 84.28; H, 9.75. Found: C, 84.28; H, 9.82.Bioorg Med Chem. Author manuscript; accessible in PMC 2015 January 01.McCullough et al.Page4.two.five. (20S) 3-Hydroxy-19,24-Dinorchola-1,3,five(ten),16-tetraen-23-ol (11)–To a option of 8 (394 mg, 0.947 mmol) in n-butanol (20 mL), at 70 , was added sodium metal (0.87 g, 38 mmol) in tiny pieces. Following all the sodium had reacted, the reaction mixture was cooled to room temperature and quenched with water, followed by saturated aqueous NH4Cl. The reaction mixture was extracted quite a few occasions with ether, the combined extracts have been dried (MgSO4) and concentrated. The residue was purified by column chromatography (SiO2, hexanes thyl acetate gradient = four:1 to two:1) to afford unreacted beginning material (91 +77.5 (c mg) followed by 11 (150 mg, 49 ) as a colorless strong. Mp 174.5?76 , 1.50, acetone); 1H NMR (acetone-d6) eight.15 (s, phenol OH), 7.04 (d, J = eight.4 Hz, 1H), 6.56 (dd, J = 2.7, eight.4 Hz, 1H), six.51 (d, J = two.7 Hz, 1H), 5.38 (br s, 1H), 3.64?.52 (m, 3H), 2.84?2.74 (m, 2H), 2.42?.28 (m, 2H), two.20?.08 (m, 1H), 1.96?.70 (m, 4H), 1.60?.30 (m, 7H), 1.ten (d, J = 7.two Hz, 3H), 0.82 (s, 3H); 13C NMR (acetone-d6) 162.8, 156.six, 139.two, 133.0, 127.six, 122.6, 117.0, 114.6, 61.four, 58.7, 49.9, 47.0, 43.0, 40.3, 37.five, 33.two, 32.0, 30.9, 30.5, 29.two, 23.7, 19.0. Anal. Calcd for C22H30O2:.