Sodium hydride → HCID 68515035, compound

HRID 2241437Notes

Reaction equation

HRID 2241437 reaction equation
[CH3:1][O:2][C:3]1[CH:27]=[CH:26][C:6]([CH2:7][N:8]2[C:12]3[N:13]=[CH:14][CH:15]=[C:16]([NH:17][CH2:18][CH2:19][N:20]4[CH2:25][CH2:24][O:23][CH2:22][CH2:21]4)[C:11]=3[CH:10]=[N:9]2)=[CH:5][CH:4]=1.[H-].[Na+].F[C:31]1[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][C:32]=1[F:40]>CN(C=O)C.CCOC(C)=O>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][N:8]2[C:12]3[N:13]=[CH:14][CH:15]=[C:16]([N:17]([C:31]4[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][C:32]=4[F:40])[CH2:18][CH2:19][N:20]4[CH2:21][CH2:22][O:23][CH2:24][CH2:25]4)[C:11]=3[CH:10]=[N:9]2)=[CH:26][CH:27]=1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 1230531,2-Difluoro-4-nitrobenzeneHCID 68514419HCID 68514419, compound

Product 1

HCID 68515035HCID 68515035, compoundYield 81.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

1-(4-Methoxybenzyl)-N-(2-morpholinoethyl)-1H-pyrazolo[3,4-b]pyridin-4-amine (0.025 g, 0.06804 mmol) was charged to a pressure tube in DMF (1 mL). NaH (0.004082 g, 0.1021 mmol) was added, and the reaction was allowed to stir at room temperature for 15 minutes. 1,2-difluoro-4-nitrobenzene (0.009389 ml, 0.08505 mmol) was added, and the reaction was stirred at room temperature for 3 hours. The reaction mixture was diluted with EtOAc (25 mL) and washed with water (15 mL). The organics were then dried with brine, dried over Na2SO4, filtered and concentrated. Purification via flash Si 5 g eluting with 1-5% MeOH/DCM to afford 28 mg (80%) of product as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.32 (d, 1H), 8.14 (m, 2H), 7.61 (t, 1H), 7.30 (m, 2H), 6.82 (d, 3H), 6.43 (d, 1H), 5.54 (s, 2H), 4.05 (t, 2H), 3.75 (s, 3H), 3.59 (t, 4H), 2.76 (t, 2H), 2.44 (m, 4H); 19F NMR (376 MHz, CDCl3) −113.92 (s, 1F); LRMS (apci pos): 307.1 (M+H)+.

Workup

  1. stirringthe reaction was stirred at room temperature for 3 hours
  2. washwashed with water (15 mL)
  3. dry with materialThe organics were then dried with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification via flash Si 5 g
  8. washeluting with 1-5% MeOH/DCM

Sources & evidence

ORD record
ord-0ac84e5ff200445b8d44e4aebf6ca638
Source dataset
uspto-grants-2010_05
Patent number
US07723330B2

Reaction notes

Loading…