Triethylamine → HCID 18327734, compound

HRID 1250255Notes

Reaction equation

HRID 1250255 reaction equation
Br[C:2]1[CH:3]=[C:4]([F:8])[CH:5]=[CH:6][CH:7]=1.[CH3:9][N:10]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:11]([CH2:13][CH:14]=[CH2:15])[CH3:12].C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(#N)C>[CH3:9][N:10]([C:16]([O:18][C:19]([CH3:20])([CH3:22])[CH3:21])=[O:17])[CH:11]([CH2:13]/[CH:14]=[CH:15]/[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[CH:3]=1)[CH3:12]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 140821-Bromo-3-fluorobenzeneHCID 15546849N-methyl-N-(tert-butoxycarbonyl)-4-penten-2-amine

Product 1

HCID 18327734HCID 18327734, compoundYield 108.4%

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
112 °C

Procedure

A 180 mL thick-walled glass pressure tube was charged with 3-bromofluorobenzene (0.95 g, 5.41 mmol), N-methyl-N-(tert-butoxycarbonyl)-4-penten-2-amine (1.08 g, 5.41 mmol), prepared as previously described, palladium(II) acetate (12.2 mg, 0.05 mmol), tri-o-tolylphosphine (65.92 mg, 0.22 mmol), triethylamine (3 mL, 21.52 mmol) and anhydrous acetonitrile (6 mL). The tube was flushed with nitrogen, sealed and the mixture was stirred and heated at 112° C. (oil bath temperature) for 66 h. The resulting mixture containing oily, brown solids, was cooled to ambient temperature and concentrated on a rotary evaporator. The resulting orange-yellow solids were diluted with water (20 mL) and extracted with CH2Cl2 (4×20 mL). The combined CH2Cl2 extracts were washed with saturated NaCl solution (30 mL), dried (Na2SO4), filtered, concentrated by rotary evaporation, and the residue was dried under high vacuum to produce a light-brown oil (1.72 g). The crude product was purified by column chromatography on silica gel (90 g), eluting with ethyl acetate-hexane (15:85, v/v). Selected fractions containing the product (Rf 0.29) were combined, concentrated by rotary evaporation and the residue was vacuum dried to give 1.36 g (85.8%) of a light-yellow oil.

Workup

  1. customprepared
  2. customThe tube was flushed with nitrogen
  3. customsealed
  4. additionThe resulting mixture containing oily
  5. temperaturebrown solids, was cooled to ambient temperature
  6. concentrationconcentrated on a rotary evaporator
  7. additionThe resulting orange-yellow solids were diluted with water (20 mL)
  8. extractionextracted with CH2Cl2 (4×20 mL)
  9. washThe combined CH2Cl2 extracts were washed with saturated NaCl solution (30 mL)
  10. dry with materialdried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated by rotary evaporation
  13. customthe residue was dried under high vacuum

Sources & evidence

ORD record
ord-f354c199752e4e9387e4f3b992d4e733
Source dataset
uspto-grants-2002_01
Patent number
US06337351B1

Reaction notes

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