Ammonium Chloride → HCID 22260279, compound

HRID 412406Notes

Reaction equation

HRID 412406 reaction equation
[CH3:1][C:2]1([CH3:23])[C:7]2[CH:8]=[C:9]([C:12]3[NH:16][C:15]([C:17]#[N:18])=[C:14]([N+:19]([O-])=O)[CH:13]=3)[CH:10]=[CH:11][C:6]=2[NH:5][C:4](=[O:22])[O:3]1.[NH4+].[Cl-]>CCO.O.C(OCC)(=O)C.[Zn]>[NH2:19][C:14]1[CH:13]=[C:12]([C:9]2[CH:10]=[CH:11][C:6]3[NH:5][C:4](=[O:22])[O:3][C:2]([CH3:1])([CH3:23])[C:7]=3[CH:8]=2)[NH:16][C:15]=1[C:17]#[N:18]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 22260266HCID 22260266, compound

Product 1

HCID 22260279HCID 22260279, compoundYield 24%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8857Ethyl AcetateSolventHCID 19096565Water ethanolSolvent

Conditions

Temperature
60 °C

Procedure

To 5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-3-nitro-1H-pyrrole-2-carbonitrile (0.14 g, 0.45 mmol) in EtOH/H2O (5:1, 20 mL:4 mL) was added Zn powder (0.35 g, 5.3 mmol) and NH4Cl (0.70 g, 13 mmol) and the mixture was heated to 60° C. for 25 min. After cooling to room temperature and stirring 24 h, the reaction mixture was diluted with ethyl acetate (100 mL) and filtered through a pad of celite. The filtrate was washed with water (50 mL) and brine (50 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (60% ethyl acetate/hexane) on silica gel gave the product as an orange foam (30 mg, 24%). 1H NMR (500 MHz, d6-DMSO) δ 1.63 (s, 6H), 5.01 (s, 2H), 5.95 (d, 1 H, J=2.9 Hz), 6.87 (d, 1 H, J=8.3 Hz), 7.48 (dd, 1 H, J=2.0, 8.3 Hz), 7.54 (d, 1 H, J=2.0 Hz), 10.30 (s, 1 H), 11.17 (d, 1 H, J=2.5 Hz). MS (ESI) [M−H]− m/z 281.

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationfiltered through a pad of celite
  3. washThe filtrate was washed with water (50 mL) and brine (50 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography (60% ethyl acetate/hexane) on silica gel

Sources & evidence

ORD record
ord-8307c39b0e67418a8c98cff42813a9b4
Source dataset
uspto-grants-2003_05
Patent number
US06562857B2

Reaction notes

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