N 30 cm3 THF beneath an N2 atmosphere. To it was added 28 mg DDQ (0.122 mmol) in five cm3 THF, and also the reaction mixture was stirred for two h at room temperature. Then it was poured into 100 cm3 ice-cold water containing 100 mg ascorbic acid and extracted with CH2Cl2 (3 ?75 cm3). Right after the combined organic extracts have been washed with sat. aq. NaHCO3, the product was dried over anhydrous Na2SO4. The solvent was evaporated (rotovap) to provide a violet-colored mixture of 3e and 5e, which was separated by radialMonatsh Chem. Author manuscript; offered in PMC 2015 June 01.Pfeiffer et al.Pagechromatography making use of CH2Cl2:CH3OH (99:1 by vol) as eluent. The doubly oxidized product (5e) was less polar and moved more quickly in the chromatography as a violet band; whereas, the a lot more polar singly oxidized product (3e) followed as a red-violet band. Yield of 5e: 17 mg (42 ); m.p.: 260 . (4Z,15Z)-9,9 -(1,2-Ethanediylidene)bis[3-ethyl-1,9-dihydro-2,7-dimethyl-1-oxodipyrrin-8butanoic acid methyl ester] (6eC38H46N4O6) Homorubin dimethyl ester 2e (40 mg, 0.061 mmol) was oxidized as in the conversion of 1e to 5e to offer crude 6e, which was purified by radial chromatography applying CH2Cl2:CH3OH (99:1 by vol). Yield: 13 mg (28 ); m.p.: 271 ; 1H NMR: = 1.ten (6H, t, J = 7.two Hz), 1.80 (4H, quint), 1.99 (6H, s), two.ten (6H, s), two.40 (4H, t, J = 7.two Hz), 2.50 (4H, q, J = 7.two Hz), two.70 (4H, t, J = 7.two Hz), three.60 (6H, s), five.80 (2H, s), 7.80 (2H, s), ten.50 (2H, brs) ppm; 13C NMR in Table 3; UV-Vis information in Table 5. Ethyl 5-(ethoxycarbonyl)-2-formyl-4-methyl-1H-pyrrole-3-propanoate (9C14H19NO) Ethyl 2,4-dimethyl-5-(ethoxycarbonyl)-1H-pyrrole-3-propanoate (726.7 g, 0.ten mol), 15 cm3 THF, 150 cm3 glacial acetic acid, and one hundred cm3 H2O were added to a 1000 cm3 round bottom flask and stirred magnetically to dissolve the pyrrole. The P2Y2 Receptor Agonist Biological Activity resolution was cooled to -5 working with an ice-salt bath, and 219.3 g ceric ammonium nitrate (CAN, 0.40 mol) was added in portions. Following the final addition, the reaction mixture was permitted to stir for two h. Then the reaction mixture was added to a 2000 cm3 separatory funnel containing 1000 cm3 water and extracted with 300 cm3 CH2Cl2. The organic extract was washed with ten aq. NaHCO3 (4 ?one hundred cm3) to eliminate excess acetic acid, separated, and dried over anhydrous Na2SO4. The solvent was removed in vacuo to offer a crude item, which was purified by column chromatography on silica gel applying CH2Cl2:CH3OH (99:1 by vol) to provide pure 9. Yield: 24.7 g (88 ); m.p.: 60?1 (Ref. [26, 42] 61?two ); 1H NMR (300 MHz): = 1.25 (3H, t, J = 7.1 Hz), 1.38 (3H, t, J = 7.1 Hz), 2.30 (3H, s), two.55 (2H, t, J = 7.1 Hz), three.06 (2H, t, J = 7.1 Hz), four.10 (2H, q, J = 7.1 Hz), 4.35 (2H, q, J = 7.1 Hz), 9.46 (1H, brs), 9.81 (1H, s) ppm; 13C NMR (75 MHz): = 9.eight, 14.1, 14.three, 18.8, 35.3, 60.6, 60.9, 124.5, 126.six, 129.9, 132.1, 160.8, 172.1, 179.5 ppm. Ethyl 5-(ethoxycarbonyl)-2-formyl-4-methyl-1H-pyrrole-3-butanoate (10C15H21NO5) Ethyl 5-(ethoxycarbonyl)-2,4-dimethyl-1H-pyrrole-3-butanoate (828.1 g, 0.10 mol) was PKC Activator Purity & Documentation dissolved in 250 cm3 acetic acid inside a 2000 cm3 round bottom flask. To it 150 cm3 THF and 200 cm3 H2O have been added, along with the answer was cooled to -5 making use of an ice-salt bath. Then, 219.three g CAN (0.40 mol) was added in portions. Right after the addition was total, the reaction mixture was stirred for three h at 0 . Work-up and purification had been accomplished following the procedure for the synthesis of 9. Yield: 24.1 g (82 ); m.p.: 48?9 ; 1H NMR (300 MHz): = 125 (3H, t, J = 7.2 Hz), 1.30 (3H, t, J =.