反应详情
EQUATION
反应方程式
REACTANTS
反应物
PRODUCTS
生成物
PROCEDURE
实验过程
A sample of 15a (38.7 mg, 0.048 mmol) was dissolved in trimethylphosphite (5.0 mL). The solution was refluxed under argon for 1.5 days. The P(OMe)3 was evaporated at reduced pressure. The residue was chromatographed (silica, CH2Cl2/MeOH, 0→5%) to yield a dark purple solid (24.6 mg, 65%): 1H NMR δ 1.64 (s, 9H), 3.15 (m, 2H), 3.32-3.36 (m, 2H), 3.43 (s, 3H), 3.47 (s, 6H), 3.50 (s, 3H), 3.81-3.87 (m, 4H), 4.84 (s, 2H), 5.44 (m, 1H), 7.35 (d, J=8.1 Hz, 2H), 8.17 (d, J=8.1 Hz, 2H), 9.10 (s, 2H), 9.40 (s, 2H), 9.50-9.51 (m, 1H), 9.73-9.74 (m, 2H), 10.30-10.31 (m, 2H); LD-MS obsd 803.7, calcd 800.3104 (C41H48N4O9P2); λabs (log ε) 407 (4.90), 504 nm; λem(λexc 407 nm) 636 nm, 702 nm. Varying amounts of a less polar purple solid (16a-Br) were isolated along with small amounts of the starting material 15a (limited characterization). Data for 16a-Br: 1H NMR δ 0.86-0.95 (m, 1H), 1.65 (s, 9H), 1.91-2.00 (m, 1H), 3.13-3.40 (m, 6H), 3.44 (s, 3H), 3.48 (s, 3H), 3.55-3.85 (m, 2H), 4.83 (s, 2H), 5.51-5.61 (m, 1H), 7.34 (d, J=8.1 Hz, 2H), 8.17 (d, J=8.1 Hz, 2H), 9.08-9.10 (m, 2H), 9.37-9.41 (m, 2H), 9.49-9.51 (m, 2H), 9.67-9.68 (m, 1H), 9.84-9.85 (m, 1H), 10.30 (s, 2H); LD-MS obsd 773.6, calcd 773.2 [(M+H)+, M=C39H42BrN4O6P2]; λabs 407, 502 nm; λem (λexc 407 nm) 634, 702 nm.
WORKUP
后处理
- temperatureThe solution was refluxed under argon for 1.5 days
- customThe P(OMe)3 was evaporated at reduced pressure
- customThe residue was chromatographed (silica, CH2Cl2/MeOH, 0→5%)