Ammonium formate → HCID 58266695, compound

HRID 1888380Notes

Reaction equation

HRID 1888380 reaction equation
Br[C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1.C([O-])=O.[NH4+]>O1CCCC1.[Zn]>[CH3:20][Si:19]([CH3:22])([CH3:21])[CH2:18][CH2:17][O:16][CH2:15][N:6]1[C:7]2[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=2[C:4]2[CH:3]=[CH:2][CH:24]=[N:23][C:5]1=2

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 58266568HCID 58266568, compound

Product 1

HCID 58266695HCID 58266695, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

A mixture of 3-bromo-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (5.6 g, 14 mmol), ammonium formate (8.8 g, 139 mmol), and zinc (9.1 g, 139 mmol) in tetrahydrofuran (85 mL) was heated at 75° C. for 10 h. The reaction was allowed to cool, filtered over a pad of celite, and washed with DCM (200 mL). The filtrate was concentrated in vacuo and then purified by flash chromatography (silica, 120 g, ISCO, 5-45% ethyl acetate in heptane) to afford the title compound as a white solid (3.6 g, 80%). 1H NMR (CDCl3, 400 MHz): 9.17 (s, 1H), 8.73 (dd, J=4.8 Hz, 1.5 Hz, 1H), 8.46 (dd, J=7.8 Hz, 1.5 Hz, 1H), 8.39 (s, 1H), 7.39 (dd, J=7.8 Hz, 4.8 Hz, 1H), 6.01 (s, 2H), 3.60 (t, J=8.0 Hz, 2H), 0.93 (t, J=8.0 Hz, 2H), −0.09 (s, 9H).

Workup

  1. temperatureto cool
  2. filtrationfiltered over a pad of celite
  3. washwashed with DCM (200 mL)
  4. concentrationThe filtrate was concentrated in vacuo
  5. custompurified by flash chromatography (silica, 120 g, ISCO, 5-45% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-a3818fae235e41ed95211dd8a06d9056
Source dataset
uspto-grants-2013_08
Patent number
US08501765B2

Reaction notes

Loading…