[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](Cl)=O)=[N:6][CH:7]=1.[C:11]1([NH:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[NH2:24])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.P(Cl)(Cl)(Cl)=O.C(=O)([O-])[O-].[Na+].[Na+]>ClCCl.O1CCOCC1.O.C(N(CC)CC)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[N:17]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[N:24]=2)=[N:6][CH:7]=1To a suspension of 5-bromopyridine-2-carbonyl chloride (10.11 g, 46 mmol), N-phenyl-1,2-diaminobenzene (8.46 g, 46 mmol) in anhydrous dichloromethane (DCM) (100 mL), was added triethylamine (TEA) at 0° C. Then the whole was stirred at room temperature (RT) for about 20 hours. The mixture was poured into water, extracted with dichloromethane (100 mL×2). The organic phase was collected, dried over sodium sulfate (Na2SO4), and passed through a pad of silica gel (hexanes/ethyl acetate 4:1). After removal of solvent, a brown oil was obtained, which was dissolved in dioxane (150 mL), phosphoryl chloride (POCl3) (25 mL) was added at 0° C., and the mixture was then heated at about 100° C. under argon overnight. Then the whole was poured into ice (200 g) after being cooled to RT, then neutralized by sodium carbonate (Na2CO3), and extracted with dichloromethane (DCM) (200 mL×2). The organic phase was dried over Na2SO4, absorbed on silica gel, and purified by a silica gel column (hexanes/ethyl acetate 4:1). The desired fraction was collected, concentrated, and reprecipitated with hexanes. After filtration and being washed with methanol, an off-white crystalline solid (Compound 1) was obtained, 4.02 g, with an overall 25% yield.
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