* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
(2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-hexaaza-2,3:12,13:22,23-tributano-7,8',17,18',27,28'-hexaethoxy-6,9:16,19:26,29-trietheno-2H,3H,12H,13H,22H,23H-hexahydro[30]annulene[ No CAS ]
Weigh 6.15g of raw materials (19mmol) and 0.068g, 0.38mmol of hexamethylphosphoric triamide (HMPA), put them in a 500mL three-necked flask, built-in thermometer, vacuum for 3 times, place in a dry ice ethanol bath, temperature control At -80C, 2.1 equiv tert-butyllithium (39.9mmol, 30.69mL, 1.3M/L) was added dropwise, and the addition was completed in 1 hour. Slowly rise to room temperature, and continue stirring at room temperature for 40 minutes. Then the reaction system was reset in a dry ice ethanol bath, kept at -80C, 16.64g DMF was slowly dripped into the system, after the dripping was completed, the dry ice ethanol bath was removed, and the mixture was stirred at room temperature for 70 min. Under ice bath, 60mL saturated aqueous ammonium chloride solution was added dropwise to the reaction system, quenched; ethyl acetate extraction 4 times, the organic phase was washed 4 times with saturated brine, the organic phase was dried, concentrated under reduced pressure, evaporated to dryness, the crude product was Purified by column chromatography, 3.29 g of white solid was obtained with a yield of 78%.
p-(N,N-diphenylamino)phenylmethyl triphenylphosphonium bromide[ No CAS ]
[ 1394287-09-2 ]
Yield
Reaction Conditions
Operation in experiment
With potassium tert-butylate; In tetrahydrofuran; at 20℃; for 3h;
To a solution of 2,5-Diethoxyterephthalaldehyde (0.85 g, 3.85 mmol) and TPA-PPh3.Br (2.31 g, 3.85 mmol) in 35 mL THF, t-BuOK (0.65 g, 5.78 mmol) was added slowly with vigorously stirring at room temperature. The reaction was completed within 3 h. The reaction mixture was poured into water and filtered to collect the orange solid (a mixture of E- and Z- isomers), which was then dried in vacuo. Then the dry solid was dissolved in 35 mL THF to reflux in the presence of catalysis amount iodine for 8 h. The mixture was added sodium bisulfite aqueous solution to remove iodine, then extracted with dichloromethane. Organic layer was dried with anhydrous sodium sulfate and removed the solvent, and was purified by column chromatography on silica gel with dichloromethane-petroleum ether (1/1; v/v) as eluent to give TPA-P-CHO (E-, yellow solid, 0.78g, yield 44%).
4-(3-(dimethylamino)propoxy)benzene-1,2-diamine[ No CAS ]
C34H44N6O4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydrogensulfite; In methanol; at 80℃; for 12h;Inert atmosphere;
Into a 50-mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 2,5-diethoxybenzene-1 ,4-dicarbaldehyde (85.00 mg, 0.382 mmol, 1 .00 equiv), 4-[3-(dimethylamino)propoxy]benzene-1 ,2-diamine (200.12 mg, 0.956 mmol, 2.5 equiv) and NaHS03 (1 19.39 mg, 1 .147 mmol, 3 equiv) in methanol (7.00 mL). The resulting solution was stirred for 12 hr at 80C. The crude product was purified by Prep-HPLC. This resulted in (3-[[2-(4-[5-[3-(dimethylamino)propoxy]-1 H-1 ,3- benzodiazol-2-yl]-2,5-diethoxyphenyl)-1 H-1 ,3-benzodiazol-5-yl]oxy]propyl)dimethylaminethe title compound. MS (ESI): m/z = 601 [M+H]+.
In N,N-dimethyl-formamide; at 0 - 80℃; for 12h;Inert atmosphere;
Into a 50-mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 2,5-dihydroxybenzene-1 ,4- dicarbaldehyde (100.00 mg, 0.602 mmol, 1 .00 equiv) and potassium methaneperoxoate potassium (251 .39 mg, 1 .806 mmol, 3 equiv) in DMF (10 ml_). Then iodoethane (234.70 mg,1 .505 mmol, 2.50 equiv) was added dropwise at 0C. The resulting solution was stirred for 12 hr at 80C. The reaction was then cooled to room temperature, quenched by the addition of water/ice and extracted with EA(3x 10 ml). The organic layer combined was washed with brine, dried over with Na2S04 and concentrated under reduced pressure. The residue was purified by prep-HPLC. This resulted in 2,5-diethoxybenzene-1 ,4-dicarbaldehyde