Triethylamine → 3-(5-amino-4-benzoyl-1H-pyrazol-1-yl)-4-methylbenzoic acid

HRID 1959490

Reaction equation

N(C1C=C(C=CC=1C)C(NOC)=[O:7])N.[NH2:15][C:16]1[N:20]([C:21]2[CH:22]=[C:23]([CH:29]=[CH:30][C:31]=2[CH3:32])[C:24](NOC)=[O:25])[N:19]=[CH:18][C:17]=1[C:33](=[O:41])[C:34]1[CH:39]=[CH:38][CH:37]=[C:36](I)[CH:35]=1.C(N(CC)CC)C>C(O)C>[NH2:15][C:16]1[N:20]([C:21]2[CH:22]=[C:23]([CH:29]=[CH:30][C:31]=2[CH3:32])[C:24]([OH:25])=[O:7])[N:19]=[CH:18][C:17]=1[C:33](=[O:41])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

Conditions

Temperature: 65 °C

Procedure

To a stirred solution of 3-hydrazino-4-methyl-benzoic acid hydrochloride 2 (242 mg, 1.19 mmol, 1.0 eq) in 25 mL of ethanol was added 2-benzoyl-3-phenylamino-acrylonitrile 4 (296 mg, 1.19 mmol, 1.0 eq, preparation: Grothasu, Davis, J. Am. Chem. Soc., 58, 1334 (1936)) and triethylamine (161 μL, 1.19 mmol, 1.0 eq) and the mixture was heated to 65° C. All solids dissolved when temperature reached 65° C. After three hours, LC-MS indicates consumption of the hydrazine. The solids were filtered to provide 3-(5-amino-4-benzoyl-pyrazol-1-yl)-4-methyl-benzoic acid 5 (95 mg, 25%) as a beige solid: HPLC (4 minute gradient) tR 2.10 min; MS m/z 322 [M+H]+; 1H NMR (DMSO-d6, 300 MHz) δ 7.99 (d, 1=7.6, 1H), 7.81 (s, 2H), 7.78 (s, 1H), 7.57 (m, 4H), 7.02 (s, 2H, NH2), 2.18 (s, 3H) ppm; 13C NMR (DMSO-d6, 75 MHz) δ 187.6, 166.3, 152.0, 141.3, 141.2, 139.6, 135.9, 131.6, 131.2, 130.1, 129.8, 128.6, 127.8, 102.6, 17.4 ppm.

Workup

dissolutionAll solids dissolved when temperature
customreached 65° C
customconsumption of the hydrazine
filtrationThe solids were filtered

Sources & evidence

ORD record: ord-0f722bff738d43159f6d09786df523f2
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08410160B2

Linked notes

Loading…