Реакция #69108

Уравнение реакции

Ammonia

NaCl

2-bromo-4-nitrotoluene

4-(Pyridine-3-yl)pyridine-2-amine

K2CO3

N,N′-dimethylethylenediamine

→

desired product

N-(2-methyl-5-nitrophenyl)-4-(pyridine-3-yl)pyridine-2-amine

Растворители

Dioxane

Условия реакции

Обработка

1. 1
   Другоеfitted with a thermometer, magnetic stirbar, and septum
2. 2
   ДругоеThe flask was evacuated
3. 3
   workup.ADDITIONback filled with N2 three times
4. 4
   workup.STIRRINGThe reaction mixture was stirred at 110° C. under N2 for 24 hours
5. 5
   Экстракцияwas then extracted with ethyl acetate (500 mL×3)
6. 6
   СушкаThe organic phase was dried over Na2SO4
7. 7
   Другоеa yellow solid was obtained after the solvent
8. 8
   Другоеwas removed under reduced pressure
9. 9
   ДругоеThe crude product was purified by column chromatography (biotage: DMC/Methanol, 1-8%, 20 CV)

Методика

4-(Pyridine-3-yl)pyridine-2-amine (8.60 g, 0.05 mol), CuI (2.39 g, 0.0125 mmol), anhydrous K2CO3 (14.0 g, 0.1 mol), KI (2.08 g, 0.0125 mol) were added to a Schlenk-type three-neck flask fitted with a thermometer, magnetic stirbar, and septum. The flask was evacuated and back filled with N2 three times. Dioxane (250 mL) and 2-bromo-4-nitrotoluene (9.82 g, 0.045 mol) were added to the flask. Finally, N,N′-dimethylethylenediamine (1.10 g, 0.0125 mol) was added by syringe at room temperature with stirring. The reaction mixture was stirred at 110° C. under N2 for 24 hours and then cooled to room temperature. Ammonia (30%, 100 mL) and saturated NaCl (400 mL), were added to the reaction mixture which was then extracted with ethyl acetate (500 mL×3). The organic phase was dried over Na2SO4 and a yellow solid was obtained after the solvent was removed under reduced pressure. The crude product was purified by column chromatography (biotage: DMC/Methanol, 1-8%, 20 CV). The desired product was obtained as a yellow solid (8.3 g, yield: 60%); 1H NMR (500 MHz, CDCl3) δ 2.49 (s, 3H), 7.36 (m, 1H), 7.15 (br., 1H), 7.35 (d, 1H), 7.38 (d, 1H), 7.52 (m, 1H), 7.88 (d, 1H), 8.55 (d, 1H), 8.60 (d, 1H), 8.76 (d, 1H), 9.28 (s, 1H), 9.50 (s, 1H). LC-MS (m/z) calculated, 307.3, found, 308.3 [M+H]+.

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