Methyl Acrylate → HCID 67530624, compound

HRID 1946701Notes

Reaction equation

HRID 1946701 reaction equation
I[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=2)[N:4]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[N:3]=1.C(N(CC)CC)C.[C:28]([O:32][CH3:33])(=[O:31])[CH:29]=[CH2:30]>CN(C=O)C.O.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH3:33][O:32][C:28](=[O:31])[CH:29]=[CH:30][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=2)[N:4]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[N:3]=1

Participants

7

Reactant 3

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 46835639tert-Butyl 3-iodo-5-nitro-1H-indazole-1-carboxylate2×

Product 1

HCID 67530624HCID 67530624, compoundYield 37%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

A solution of tert-butyl 3-iodo-5-nitro-1H-indazole-1-carboxylate (Intermediate 44, 4.6 g; 11.8 mmol) in DMF (76 ml) and water (12 ml) was treated with triethylamine (12 ml; 86 mmol), methyl acrylate (10.4 ml; 115 mmol) and tetrabutyl ammonium iodide (8.6 g; 23 mmol). The mixture was degassed and then dichlorobis(triphenylphosphine)palladium (II), (1.68 g; 2.4 mmol) was added. The mixture was heated to 50° C. for 18 hours and the volatile solvent removed in vacuo. The mixture was poured into water (600 ml) and extracted with EtOAc. The combined organic extracts were washed with water, dried over sodium sulfate, filtered and the solvent removed in vacuo. The residue was purified by column chromatography (silica) eluting with petroleum ether containing increasing amounts of EtOAc to give tert-butyl 3-(3-methoxy-3-oxoprop-1-enyl)-5-nitro-1H-indazole-1-carboxylate as a light brown solid (1.5 g, 37%). A solution of this residue (200 mg; 0.58 mmol) in methanol (100 ml) was treated with palladium (100 mg, 5% on C). The mixture was stirred under hydrogen for 18 hours, filtered and the solvent removed in vacuo. The residue was purified by column chromatography (silica) eluting with petroleum ether containing increasing amounts of EtOAc to give the title compound as an off-white solid.

Workup

  1. customThe mixture was degassed
  2. additiondichlorobis(triphenylphosphine)palladium (II), (1.68 g; 2.4 mmol) was added
  3. customthe volatile solvent removed in vacuo
  4. additionThe mixture was poured into water (600 ml)
  5. extractionextracted with EtOAc
  6. washThe combined organic extracts were washed with water
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. customthe solvent removed in vacuo
  10. customThe residue was purified by column chromatography (silica)
  11. washeluting with petroleum ether containing
  12. temperatureincreasing amounts of EtOAc

Sources & evidence

ORD record
ord-1c04e4e9256948e389e98322467bf182
Source dataset
uspto-grants-2013_03
Patent number
US08399448B2

Reaction notes

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