17 (m, 1H), 4.52?.63 (m, 1H), 6.57 (m, 1H), 6.92 (m, 1H). 13C NMR (CDCl3, 50 MHz) 14.0, 20.two, 20.six, 22.6, 24.eight, 24.9, 26.7, 29.two, 29.2, 29.three, 29.four, 29.five, 30.8, 31.1, 31.eight, 38.9, 62.6, 64.0, 64.two, 64.5, 77.three, 80.7, 100.two, one hundred.four, 169.9, 171.four. Rf (CHCl3/EtOAc five:2) 0.22. Anal. Cald for C20H39NO4: C, 67.19; H, ten.99; N, 3.92; Discovered: C, 67.39; H, 10.92; N, three.79. MS MH+ C20H39NO4H Calcd: 358.2964, Discovered: 358.2946. four.three. General procedures for phosphorylation from the 1,2-disubstituted glyceric acid derivatives 4.three.1. 3-(Dodecyloxy)-2-[10-(7mercapto-4methylcoumarin-7yl)decanoyl)oxy]-3-(oxopropyl)phosphocholine (19)–To a solution of 13 (0.2802 g, 0.46 mmol) in 40 mL freshly distilled benzene partially submerged in an ice bath was added 2-chloro-2-oxo-1,2,3dioxaphospholane (130 L, 1.four mmol) followed by a remedy of triethylamine (80 L, 0.57 mmol) in 10 mL benzene, added drop-wise. Eight hours later much more phosphorylating agent was added (150 L, 1.6 mmol) plus the reaction mixture was stirred at space temperature overnight. The precipitate that formed was filtered, plus the filtrate was evaporated to offer a white waxy residue. This residue was dispersed in 25 mL of anhydrous acetonitrile, along with the dispersion was transferred to stress bottle and cooled to -10 . To this mixture was added excess trimethylamine (4 mL), the pressure bottle was sealed, heated to 65 , and kept for 24 h. Cooling to room temperature and later in an ice-bath led to formation of a white precipitate.169566-81-8 custom synthesis This precipitate was filtered, washed with three x 20 mL cold acetonitrile and chromatographed on silica gel having a remedy of CHCl3/MeOH/H2O (65:25:4). The combined CH3CN phase was evaporated to give an oily residue, which was dissolved inside the mixture of CHCl3/MeOH/H2O (65:25:four) and purified on a separate silica gel column packed with CHCl3/MeOH (four:1) and eluted with CHCl3/MeOH/H2O (65:25:four). The fractions containing the solution were collected, evaporated, dispersed in benzene and freeze-dried toNIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptTetrahedron. Author manuscript; out there in PMC 2015 May 13.Rosseto and HajduPagegive 19 as a white strong (inside a combined yield of 0.1695 g, 48 ). IR (CHCl3): 3330, 1731 br, 1632, 1206 cm-1; 1H NMR (CDCl3+CD3OD, 200 MHz) 0.79 (br t, 3H), 1.18 (br s, 26H), 1.58 (m, 8H), 2.21 (t, 2H, J = 7.2 Hz), two.35 (s, 3H), 2.91 (t, 2H, J = six.eight Hz), 3.15 (br s, 9H), 4.07 (m, 4H), 4.25?.38 (m, 4H), 4.87 (m, 1H), six.15 (s, 1H), 7.08?.27 (m, 3H). 13C NMR (CDCl3, 50 MHz) 8.six, 14.1, 18.5, 22.6, 24.7, 25.eight, 28.five, 28.7, 28.eight, 29.0, 29.2, 29.three, 29.2,2-Dibenzylpropane-1,3-diol Order five, 29.PMID:23664186 six, 31.8, 32.1, 33.9, 45.7, 54.four, 59.8, 64.five, 65.six, 66.0, 72.two, 113.6, 116.eight, 122.eight, 124.five, 143.7, 152.3, 153.8, 160.six, 169.2, 173.1. 31P NMR (CDCl3, 160 MHz, pyrophosphate ref. ext.) -2.91. Rf (CHCl3/MeOH/H2O 65:25:4) 0.45. Anal. Cald for C40H66NO10PS?H2O: C, 58.59; H, 8.60; N, 1.71; Found: C, 58.91; H, eight.47; N, 1.94. MS MH+ C40H66NO10PSH Calcd: 784.4223, Discovered: 784.4206. []D20 -6.4?(c 1.09, CHCl3/MeOH four:1). 4.3.two. 3-(dodecylamino)-2-[(10-(7-mercapto-4methylcoumarin-7yl)decanoyl)oxy]-3-(oxopropyl)-phosphocholine (20) Route I–To a suspension of 17 in 25 mL freshly distilled benzene, partially submerged in an icewater bath was added 2-chloro-2-oxo-1,2,3-dioxaphospholane (70 L, 0.57 mmol) followed by a answer of triethylamine (82 L, 0.60 mmol) in five mL benzene drop-wise. Six hours later, more phosphorylating agent was added (30 L, 0.32 mmol) to this mixture. The reaction was stirred at area tem.