Triethylamine → HCID 58136738, compound

HRID 877169Notes

Reaction equation

HRID 877169 reaction equation
[C:1]([O:5][CH2:6][CH3:7])(=[O:4])[CH:2]=[CH2:3].Br[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-])=O)[C:10]=1[CH3:18].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[Cl-].[NH4+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:15][C:11]1[C:10]([CH3:18])=[C:9]([CH2:3][CH2:2][C:1]([O:5][CH2:6][CH3:7])=[O:4])[CH:14]=[CH:13][CH:12]=1

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 25517Ammonium ChlorideHCID 80271Tri-o-tolylphosphineHCID 1235372-Bromo-6-nitrotoluene

Product 1

HCID 58136738HCID 58136738, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
125 °C

Procedure

Under argon, 10.844 g (108 mmol) of ethyl prop-2-enoate were added dropwise to a solution of 7.8 g (36.1 mmol) of 1-bromo-2-methyl-3-nitrobenzene, 25 ml (180.5 mmol) of triethylamine, 2.197 g (7.22 mmol) of tri-2-tolylphosphine and 810 mg (3.6 mmol) of palladium(II) acetate in 200 ml of DMF, and the mixture was then stirred at 125° C. for 36 h. After cooling to room temperature, the reaction mixture was stirred with saturated aqueous ammonium chloride solution and the organic phase was separated off. The aqueous phase was extracted three times with tert-butyl methyl ether, and the combined organic phases were washed with saturated sodium chloride solution and dried over sodium sulfate. After filtration, the solvent was removed to dryness under reduced pressure. The residue obtained was purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 3:1). This gave 6.6 g (27.2 mmol, content 97%, 75% of theory) of the intermediate ethyl (2E)-3-(2-methyl-3-nitrophenyl)prop-2-enoate as a colorless solid. 6.6 g (27.2 mmol, content 97%) of this solid were dissolved in 200 ml of ethanol, 500 mg of palladium on carbon (10%) were added at room temperature and the mixture was hydrogenated under atmospheric pressure overnight. After the reaction had gone to completion, the reaction solution was filtered through kieselguhr and the filtrate obtained was concentrated under reduced pressure. This gave 5.47 g (26.38 mmol, content 97%, 97% of theory) of the title compound as a colorless solid.

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe organic phase was separated off
  3. extractionThe aqueous phase was extracted three times with tert-butyl methyl ether
  4. washthe combined organic phases were washed with saturated sodium chloride solution
  5. dry with materialdried over sodium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was removed to dryness under reduced pressure
  8. customThe residue obtained
  9. customwas purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 3:1)
  10. dissolution6.6 g (27.2 mmol, content 97%) of this solid were dissolved in 200 ml of ethanol
  11. addition500 mg of palladium on carbon (10%) were added at room temperature
  12. customwas hydrogenated under atmospheric pressure overnight
  13. filtrationthe reaction solution was filtered through kieselguhr
  14. customthe filtrate obtained
  15. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-393d49c0975143129500f59c3d0b981f
Source dataset
uspto-grants-2015_03
Patent number
US08987256B2

Reaction notes

Loading…