Ammonium Chloride → 3-methyl-5-(1-(2-methylallyl)-1H-pyrazol-4-yl)aniline

HRID 595160Notes

Reaction equation

[Cl-].[NH4+].[CH3:3][C:4]1[CH:5]=[C:6]([C:13]2[CH:14]=[N:15][N:16]([CH2:18][C:19]([CH3:21])=[CH2:20])[CH:17]=2)[CH:7]=[C:8]([N+:10]([O-])=O)[CH:9]=1>C(O)C.O.[Fe]>[CH3:3][C:4]1[CH:9]=[C:8]([CH:7]=[C:6]([C:13]2[CH:14]=[N:15][N:16]([CH2:18][C:19]([CH3:21])=[CH2:20])[CH:17]=2)[CH:5]=1)[NH2:10]

Participants

Conditions

Temperature: 70 °C

Procedure

Iron (1.57 g, 28.2 mmol) and saturated aqueous ammonium chloride (11 mL) were added to a solution of 4-(3-methyl-5-nitrophenyl)-1-(2-methylallyl)-1H-pyrazole (2.42 g, 9.41 mmol) in ethanol (7 mL) and water (11 mL). The mixture was heated at 70° C. for 18 h, then allowed to cool to room temperature, passed through CELITE, washed with methanol, and concentrated under reduced pressure. The residue was diluted with EtOAc and washed with water, saturated aqueous sodium bicarbonate and brine. The organic layers were separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give 3-methyl-5-(1-(2-methylallyl)-1H-pyrazol-4-yl)aniline. MS ESI calc'd. for C14H18N3 [M+H]+ 228. found 228. 1H NMR (500 MHz, DMSO-d6) δ 7.92 (s, 1H), 7.68 (s, 1H), 6.52 (s, 2H), 6.21 (s, 1H), 4.92 (s, 2H), 4.87 (s, 1H), 4.70 (s, 1H), 4.66 (s, 2H), 2.14 (s, 3H). 1.60 (s, 3H).

Workup

temperatureto cool to room temperature
washwashed with methanol
concentrationconcentrated under reduced pressure
additionThe residue was diluted with EtOAc
washwashed with water, saturated aqueous sodium bicarbonate and brine
customThe organic layers were separated
dry with materialdried over anhydrous magnesium sulfate
filtrationfiltered
concentrationconcentrated under reduced pressure

Sources & evidence

ORD record: ord-9604393dc4c74b63a695d79ad5dc8b95
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09242984B2

Reaction notes

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