To a suspension of 4-(4-Nitrophenyl)-1H-pyrazole (8.3 g, 43.88 mmol) in MeOH/DME (2:1 v/v) was added 10percent Pd/C (wet, 415 mg). The reaction flask was purged with vacuum then filled with H2 from a balloon. This was done a total of 3 times. The reaction mixture was stirred at rt and checked by LC-MS for formation of the amine. After stirring for 2.5 at rt, LC-MS and tlc showed that there is a minor amount of SM in the reaction. An additional amount of catalyst (200 mg) was added to the reaction mixture and the reaction vessel was filled with H2 as before. The reaction was checked after 2h for disappearance of the remaining SM. At this time, the reaction was complete. The mixture was filtered on Celite and the Celite was washed with MeOH. The solvent was removed in vacuo to give 6.59 g (94percent) of a yellow solid. ‘H NIVIR (400 MHz, DMSO-d6) ö 12.68 (b, 1H), 7.80 (s, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H), 4.97 (s, 2H). MS (ES+) m/e 160 (M+H)+.
94%
With palladium 10% on activated carbon; hydrogen In methanol; 1,2-dimethoxyethane at 20℃; for 2 h;
[0092] To a suspension of 4-(4-Nitrophenyl)-lH-pyrazole (8.3 g, 43.88 mmol) in MeOH/DME (2: 1 v/v) was added 10percent Pd/C (wet, 415 mg). The reaction flask was purged with vacuum then filled with from a balloon. This was done a total of 3 times. The reaction mixture was stirred at rt and checked by LC-MS for formation of the amine. After stirring for 2.5 at rt, LC-MS and tic showed that there is a minor amount of SM in the reaction. An additional amount of catalyst (200 mg) was added to the reaction mixture and the reaction vessel was filled with as before. The reaction was checked after 2h for disappearance of the remaining SM. At this time, the reaction was complete. The mixture was filtered on Celite and the Celite was washed with MeOH. The solvent was removed in vacuo to give 6.59 g (94percent) of a yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 12.68 (b, 1H), 7.80 (s, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H), 4.97 (s, 2H). MS (ES+) m/e 160 (M+H)+.
Reference：
[1] Patent: WO2016/210331, 2016, A1, . Location in patent: Paragraph 0087; 0088
[2] Patent: WO2016/210330, 2016, A1, . Location in patent: Paragraph 0091-0092
[3] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1987, vol. 26, # 1-12, p. 616 - 619
With palladium 10% on activated carbon; hydrogen; at 20.0℃;
To a suspension of 4-(4-Nitrophenyl)-1H-pyrazole (8.3 g, 43.88 mmol) in MeOH/DME (2:1 v/v) was added 10% Pd/C (wet, 415 mg). The reaction flask was purged with vacuum then filled with H2 from a balloon. This was done a total of 3 times. The reaction mixture was stirred at rt and checked by LC-MS for formation of the amine. After stirring for 2.5 at rt, LC-MS and tlc showed that there is a minor amount of SM in the reaction. An additional amount of catalyst (200 mg) was added to the reaction mixture and the reaction vessel was filled with H2 as before. The reaction was checked after 2h for disappearance of the remaining SM. At this time, the reaction was complete. The mixture was filtered on Celite and the Celite was washed with MeOH. The solvent was removed in vacuo to give 6.59 g (94%) of a yellow solid. ?H NIVIR (400 MHz, DMSO-d6) oe 12.68 (b, 1H), 7.80 (s, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H), 4.97 (s, 2H). MS (ES+) m/e 160 (M+H)+.
94%
With palladium 10% on activated carbon; hydrogen; In methanol; 1,2-dimethoxyethane; at 20.0℃; under 1838.94 Torr; for 2.0h;
[0092] To a suspension of 4-(4-Nitrophenyl)-lH-pyrazole (8.3 g, 43.88 mmol) in MeOH/DME (2: 1 v/v) was added 10% Pd/C (wet, 415 mg). The reaction flask was purged with vacuum then filled with from a balloon. This was done a total of 3 times. The reaction mixture was stirred at rt and checked by LC-MS for formation of the amine. After stirring for 2.5 at rt, LC-MS and tic showed that there is a minor amount of SM in the reaction. An additional amount of catalyst (200 mg) was added to the reaction mixture and the reaction vessel was filled with as before. The reaction was checked after 2h for disappearance of the remaining SM. At this time, the reaction was complete. The mixture was filtered on Celite and the Celite was washed with MeOH. The solvent was removed in vacuo to give 6.59 g (94%) of a yellow solid. 1H NMR (400 MHz, DMSO-d6) delta 12.68 (b, 1H), 7.80 (s, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H), 4.97 (s, 2H). MS (ES+) m/e 160 (M+H)+.
With hydrogen;
Intermediate 259 corresponds with CAS: 114474-26-9. Hydrogenation of the nitro group according to wellk-known methods afforded intermediate 260.
90 mg
With palladium 10% on activated carbon; hydrogen; In methanol; at 20.0℃; for 4.0h;
A mixture containing 4-(4-nitrophenyl)-1H-pyrazole (commercially available from Combi-Blocks, 110 mg), 10% Pd/C (11 mg)and methanol (5 mL) was stirred at room temperature for 4 hours under a hydrogen atmosphere. Insoluble substances in the reaction mixture were filtered off. Then, the filtrate was concentrated under a reduced pressure, and thereby 4-(1H-pyrazol-4-yl)aniline (90 mg)as a brown solid was obtained.
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