Cl.[Cl:2][CH2:3][CH2:4][CH2:5][NH:6][C:7]1[C:12]([N+:13]([O-])=O)=[C:11]([O:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[N:10]=[C:9]([CH3:23])[C:8]=1[CH3:24].[Br-].[Br-].C([N+]1C=CC(C2C=C[N+](CCCCCCCC)=CC=2)=CC=1)CCCCCCC.C(=O)([O-])[O-].[K+].[K+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>O.ClCCl>[Cl:2][CH2:3][CH2:4][CH2:5][NH:6][C:7]1[C:8]([CH3:24])=[C:9]([CH3:23])[N:10]=[C:11]([O:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:12]=1[NH2:13]N-(3-chloropropyl)-2,3-dimethyl-5-nitro-6-phenoxypyridin-4-amine hydrochloride (12.62 g, 33.72 mmol), 1,1′-di-n-octyl-4,4′-bipyridinium dibromide (dioctyl viologen) (910 mg, 1.69 mmol), dichloromethane (227 mL), water (28 mL) and potassium carbonate (2.33 g, 16.9 mmol) were added sequentially to a 1 L round bottom flask. The reaction mixture was allowed to stir under nitrogen. A solution of of potassium carbonate (23.30 g, 168.6 mmol) and sodium dithionite (26.42 g, 174.1 mmol) in water (114 mL) was added to the reaction mixture. The reaction mixture was heated at reflux for about 2.5 hr and then allowed to cool to ambient temperature. The layers were separated. The aqueous layer was extracted with dichloromethane (100 mL). The combined organics were dried over sodium sulfate, filtered and then concentrated under reduced pressure to provide N4-(3-chloropropyl)-5,6-dimethyl-2-phenoxypyridine-3,4-diamine as a brown sludge. This material was used directly in the next step.
読み込み中…
