Acetic Anhydride → HCID 11257063, compound

HRID 1836713Notes

Reaction equation

HRID 1836713 reaction equation
[C:1]1([S:7]([N:10]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[CH:12]=[C:11]2[CH:19](OC(=O)C)[CH:20]=[CH2:21])(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:26]([O:29][C:30](=O)C)(=[O:28])[CH3:27].C(N(CC)CC)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C]=O>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]1([S:7]([N:10]2[C:11]3[CH:19]=[CH:20][CH:21]=[C:30]([O:29][C:26](=[O:28])[CH3:27])[C:12]=3[C:13]3[C:18]2=[CH:17][CH:16]=[CH:15][CH:14]=3)(=[O:8])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 5

HCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 11725738Acetic acid 1-(1-benzenesulfonyl-1H-indol-2-yl)-allyl esterHCID 178418416HCID 178418416, compound2×

Product 1

HCID 11257063HCID 11257063, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

An autoclave was charged under an argon flow with 1.066 g of acetic acid 1-(1-benzenesulfonyl-1H-indol-2-yl)-allyl ester (3.0 mmol, oil, crude quality), 0.57 ml of acetic anhydride (6.0 mmol), 0.92 ml of triethylamine (6.6 mmol) and 2.5 ml of a catalyst solution prepared from 6.73 mg of palladium acetate (0.030 mmol) and 78.7 mg of triphenylphosphine (0.30 mmol) in 25 ml of toluene. Then the autoclave was sealed, pressurized three times with 20 bar of carbon monoxide and vented, and finally pressurized with 50 bar of carbon monoxide. The reaction mixture was stirred magnetically and heated at 90° C. for 20 h. After cooling and venting the autocave, the dark reaction mixture was poured onto ice water and the biphasic solution stirred vigorously for 1 h. The aqueous phase was extracted with 20 ml of toluene, whereas the toluene phase was extracted in a separatory funnel with 10 ml of water and 10 ml of brine. The combined toluene phases were dried on sodium sulfate and finally rotary evaporated (47° C., 10 mbar). The resulting brown residue was purified by chromatography on silica gel (eluent: cyclohexane/tbutyl methyl ether 2:1 vol/vol) to afford 960 mg (88%) of acetic acid 9-benzenesulfonyl-9H-carbazol-4-yl ester as a light brown oil.

Workup

  1. customThen the autoclave was sealed
  2. temperatureAfter cooling
  3. customthe dark reaction mixture
  4. additionwas poured onto ice water
  5. stirringthe biphasic solution stirred vigorously for 1 h
  6. extractionThe aqueous phase was extracted with 20 ml of toluene, whereas the toluene phase
  7. extractionwas extracted in a separatory funnel with 10 ml of water and 10 ml of brine
  8. dry with materialThe combined toluene phases were dried on sodium sulfate
  9. customfinally rotary evaporated (47° C., 10 mbar)
  10. customThe resulting brown residue was purified by chromatography on silica gel (eluent: cyclohexane/tbutyl methyl ether 2:1 vol/vol)

Sources & evidence

ORD record
ord-be00486c54554da9a965ef86c51220c1
Source dataset
uspto-grants-2004_08
Patent number
US06777559B2

Reaction notes

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