Dimethylformamide → 4-(4-bromo-2-methylphenyl)-1-ethyl-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazolo[3,4-b]pyridin-6(7H)-one

HRID 1748778Notes

Reaction equation

[Br:1][C:2]1[CH:18]=[CH:17][C:5]([CH:6]=[C:7]2[C:12](=[O:13])OC(C)(C)OC2=O)=[CH:4][CH:3]=1.[CH2:19]([N:21]1[C:25]([NH2:26])=[CH:24][C:23]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][N:28]=2)=[N:22]1)[CH3:20].[CH3:33]N(C=O)C>O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:6]2[CH2:7][C:12](=[O:13])[NH:26][C:25]3[N:21]([CH2:19][CH3:20])[N:22]=[C:23]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][N:28]=4)[C:24]2=3)=[C:17]([CH3:33])[CH:18]=1

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of 5-(4-bromobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (1.1 g, 3.54 mmol, Preparation W.1) and 1-ethyl-3-(pyridin-2-yl)-1H-pyrazol-5-amine (0.67 g, 3.54 mmol, prepared using B from Example #2, step A with ethyl hydrazine oxalate) in DMF (5 mL) was heated under nitrogen at about 60° C. for about 30 min. The reaction was cooled to rt, diluted with water (20 mL) and then the product was filtered off and rinsed with water (˜20 mL). The product was dried under vacuum at about 50° C. for about 16 h to yield 4-(4-bromo-2-methylphenyl)-1-ethyl-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazolo[3,4-b]pyridin-6(7H)-one as a tan solid (1.41 g, 3.54 mmol, 80%). LC-MS (Table 1, Method g) Rt=2.11 min, m/z 397/399 (M+H)+; 1H NMR (400 MHz, DMSO-d6) δ 10.88 (s, 1H), 8.44-8.41 (m, 1H), 7.84 (dt, J=8.0, 1.1 Hz, 1H), 7.77-7.69 (m, 1H), 7.43-7.36 (m, 2H), 7.21-7.17 (m, 1H), 7.10-7.04 (m, 2H), 6.63 (d, J=6.6 Hz, 1H), 4.22-4.03 (m, 2H), 3.14 (dd, J=16.0, 7.8 Hz, 1H), 2.53 (d, J=26.1 Hz, 1H), 1.33 (t, J=7.2 Hz, 3H).

Workup

temperatureThe reaction was cooled to rt
filtrationthe product was filtered off
washrinsed with water (˜20 mL)
customThe product was dried under vacuum at about 50° C. for about 16 h

Sources & evidence

ORD record: ord-71bf96038a004ab2b7c8a5c46fc21092
Source dataset: uspto-grants-2015_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09150592B2

Reaction notes

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