95% |
With hydrogen;palladium on activated charcoal; In tetrahydrofuran; methanol; at 20℃; |
The thus obtained nitro comound was hydrogenated at room temperature using Pd/C in MeOH/THF. The reaction solution was filtered through kieselguhr and rinsed with MeOH, and the filtrate was subsequently evaporated. The residue was digested with diethyl ether, filtered off with suction, rinsed with diethyl, ether and dried overnight at 40C under reduced pressure. Yield : 37.14 g (95%) of 5b, pale-brown crystals |
95% |
With hydrogen;palladium on activated charcoal; In tetrahydrofuran; methanol; at 20℃; |
Compound 5 is hydrogenated with Pd/C in [METHANOL/TETRAHYDROFURANE] at room temperature. The reaction mixture is filtered over kieselguhr, the residue washed with methanol and the filtrate evaporated. The residue is digested with diethyl ether, filtered by suction, washed with diethyl ether and dried in vacuum at 40 [C] overnight to yield 37.14 g (95 %) light brownish crystals of 6. |
95% |
With hydrogen;palladium on activated charcoal; In tetrahydrofuran; methanol; at 20℃; |
b) Compound 5 is hydrogenated at room temperature using Pd/C in MeOH/THF. The reaction solution is filtered through kieselguhr and rinsed with MeOH, and the filtrate is subsequently evaporated. The residue is digested with diethyl ether, filtered off with suction, rinsed with diethyl ether and dried overnight at 40C under reduced pressure. Yield : 37.14 g (95%) of 6, pale-brown crystals |
95% |
With hydrogen;palladium 10% on activated carbon; In ethyl acetate; under 2068.65 Torr; for 3.5h; |
A solution of 3- (4-nitrophenoxy)pyridine g, 23.13 mmol) in EtOAc (100 mL) in a 250 ml Parr bottle was purged with nitrogen. To this solution was added EtOAc-moistened 10% Pd/C catalyst (500 mg, 10% by weight). The reaction flask was placed in a Parr hygrogenation apparatus, purged with nitrogen (5x), evacuated, and then pressurized to 40 psi with hydrogen and shaken for 3.5 h. The reaction mixture was then purged with nitrogen, and filtered through a pad of Celite , rinsing with ethyl acetate (3x) and ethanol (3x). The filtrate was evaporated at reduced pressure to give a brown crystalline residue. The residue was stirred in diethyl ether at room temperature for 16 h and then filtered to provide 4.11 g (95%) of the desired product as light brown crystals. (at)H-NMR (DMSO-d6) No. 8.21 (m, 2H), 7.30 (ddd, J = 8.4,4.6, 0.7 Hz, 1 H), 7.18 (ddd, J = 8.4, 2.9, 1.4 Hz, 1 H), 6.79 (d, J = 8.8 Hz, 2H), 6.58 (d, J = 9.0 Hz, 2H), 5.05 (br s, 2H) ; MS LC-MS [M+H]+ = 187, RT = 1.03 min. |
36% |
With iron; ammonium chloride; In tetrahydrofuran; methanol; water; at 80℃; for 3h; |
4-(Pyridin-3-yl)oxy-l -nitrobenzene prepared in Step A was dissolved in the mixture of water (100 mL), tetrahydrofuran (100 mL) and methanol (100 mL). Iron powder (103 g, 1.84 mol) and ammonium chloride (99 g, 1.84 mol) were added thereto, and the mixture was stirred for 3 h at 80 C using a mechanical stirrer. After completion of the reaction, the reaction mixture was filtered through a cellite, washed with methanol, and concentrated under reduced pressure. The solid thus obtained was filtered, washed with ether, and dried to give the title compound (17 g, Yield 36%). Mass[M+H] : 186 (M+l) |
36% |
With iron; ammonium chloride; In tetrahydrofuran; methanol; at 80℃; for 3h; |
The compound thus obtained was dissolved using water (100ml), tetrahydrofuran (100ml) and methanol (100ml). Iron powder (103g, 1.84 mol) and ammonium chloride (99g, 1.84 mol) were added thereto, and the mixture was stirred using a mechanical stirrer for 3 h at 80 "C . After completion of the reaction, the reaction solution was filtered through a celite, washed with methanol, and concentrated.The resulting solid was filtered, washed with ether, and dried to give 4-(pyridin-3- yloxy)-phenylamine ( 17g, Yield 36%). |
36% |
With water; iron; ammonium chloride; In tetrahydrofuran; methanol; at 80℃; for 3h; |
4-(Pyridin-3-yl)oxy-1-nitrobenzene prepared in Step A was dissolved in the mixture of water (100 mL), tetrahydrofuran (100 mL) and methanol (100 mL). Iron powder (103 g, 1.84 mol) and ammonium chloride (99 g, 1.84 mol) were added thereto, and the mixture was stirred for 3 h at 80 C. using a mechanical stirrer. After completion of the reaction, the reaction mixture was filtered through a cellite, washed with methanol, and concentrated under reduced pressure. The solid thus obtained was filtered, washed with ether, and dried to give the title compound (17 g, Yield 36%). |
|
With iron; ammonium chloride; In tetrahydrofuran; water; at 80℃; for 3h; |
1-Chloro-4-nitrobenzene (40 g, 0.25 mol) and 3-hydroxypyridine (36 g, 0.38 mol) were dissolved in N,N-dimethylformamide (100 ml). Potassium carbonate (52.6 g, 0.38 mol) was added thereto, and the mixture was stirred for 20 h at 100 C. Water was added to the reaction solution, which was then extracted with ethyl acetate. The extract was washed with saturated sodium chloride solution, and dried over anhydrous magnesium sulfate to give 3-(4-nitro-phenoxy)-pyridine.The compound thus obtained was dissolved using water (100 ml), tetrahydrofuran (100 ml) and methanol (100 ml). Iron powder (103 g, 1.84 mol) and ammonium chloride (99 g, 1.84 mol) were added thereto, and the mixture was stirred using a mechanical stirrer for 3 h at 80 C. After completion of the reaction, the reaction solution was filtered through a celite, washed with methanol, and concentrated. The resulting solid was filtered, washed with ether, and dried to give 4-(pyridin-3-yloxy)-phenylamine (17 g, Yield 36%). |
|
With iron; ammonium chloride; In tetrahydrofuran; methanol; water; at 80℃; for 3h; |
(Step 1)1-Chloro-4-nitrobenzene (40 g, 0.25 mol) and 3-hydroxypyridine (36 g, 0.38 mol) were dissolved in N,N-dimethylformamide (100 ml). Potassium carbonate (52.6 g, 0.38 mol) was added, and the mixture was stirred for 20 h at 100. Water was added, and the resulting mixture was extracted with ethyl acetate, washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate to give 3-(4-nitro-phenoxy)-pyridine.Thus obtained compound was dissolved using water (100 ml), tetrahydrofuran (100 ml) and methanol (100 ml). Iron dust (103 g, 1.84 mol) and ammonium chloride (99 g, 1.84 mol) were added, and the mixture was stirred using a mechanical stirrer for 3 h at 80. After completion of the reaction, the reaction mixture was filtered through celite, washed with methanol and concentrated. The resulting solid was filtered, washed with ether and dried to give 4-(pyridin-3-yloxy)-phenylamine (17 g, Yield 36%). |
|
With hydrogen;palladium on activated charcoal; In methanol; for 2.5h; |
3-(4-nitrophenoxy)pyridine (4.1 g, 18.9 mmol) was dissolved in MeOH (50 mL) and hydrogenated in the presence of a catalytic amount of Pd/C with a balloon of Hydrogen for 2.5 h. Pd/C was removed by filtration and the filtrate was evaporated to dryness under reduced pressure to afford 4-(pyridin-3-yloxy)aniline as a grey solid. |