Ammonium formate → HCID 178463787, compound

HRID 1518043Notes

Reaction equation

HRID 1518043 reaction equation
[CH2:1]([N:3]([CH2:27][CH3:28])[C:4]1[C:5]([N+:24]([O-])=O)=[CH:6][C:7]([N+:21]([O-])=O)=[C:8]([NH:10][C:11](=O)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[O:18][CH3:19])[CH:9]=1)[CH3:2].C([O-])=O.[NH4+]>O1CCOCC1.CO.[Pd]>[NH2:24][C:5]1[C:4]([N:3]([CH2:27][CH3:28])[CH2:1][CH3:2])=[CH:9][C:8]2[NH:10][C:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=3[O:18][CH3:19])=[N:21][C:7]=2[CH:6]=1

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 59530560HCID 59530560, compound

Product 1

HCID 178463787HCID 178463787, compoundYield 61%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
75 °C

Procedure

To the solution of 5-(diethylamino)-2,4-dinitro-1-(2-methoxybenzoyl)aminobenzene (388 mg, 1.0 mmol) in 10 mL of 1,4-dioxane and 10 mL of methanol, was added ammonium formate (1.5 g) and 10% Pd/C (200 mg) under nitrogen atmosphere. The reaction mixture was stirred for 30 min. The Pd/C and excess ammonium formate were filtered. Conc. HCl (10 mL) was added to the filtrate. After heating at 75° C. for 18 h, the reaction mixture was basified to pH 8 with saturated K2CO3 solution. The reaction mixture was diluted with 200 mL of ethyl acetate, washed with brine, and dried over anhydrous MgSO4. The reaction mixture was filtered and concentrated in vacuo to afford the crude product (280 mg, 90% yield). The crude product was then purified by column chromatography on silica gel using EtOAc as the eluant to afford the desired product (188 mg, 61% yield) as a brown solid: 1H-NMR (300 MHz, CDCl3) δ 1.01 (t, 6H, J=7.2 Hz), 3.01 (q, 4H, J=7.2 Hz), 4.05 (s, 3H), 6.92 (s, 1H), 7.03 (d, 1H, J=8.1 Hz), 7.11 (t, 1H, J=8.1 Hz), 7.36 (t, 1H, J=6.9), 7.41 (s, 1H), 8.52 (d, 1H, J=7.8 Hz); ESI MS m/z 311.2 [M+H]+.

Workup

  1. filtrationThe Pd/C and excess ammonium formate were filtered
  2. additionConc. HCl (10 mL) was added to the filtrate
  3. additionThe reaction mixture was diluted with 200 mL of ethyl acetate
  4. washwashed with brine
  5. dry with materialdried over anhydrous MgSO4
  6. filtrationThe reaction mixture was filtered
  7. concentrationconcentrated in vacuo
  8. customto afford the crude product (280 mg, 90% yield)
  9. customThe crude product was then purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-75b7de5514b44508af3a955c37080fd2
Source dataset
uspto-grants-2012_07
Patent number
US08232410B2

Reaction notes

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