Carbon Dioxide → Skatole

HRID 990297Notes

Reaction equation

HRID 990297 reaction equation
[CH2:1]([NH:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1I)[CH:2]=[CH2:3].C(N(CC)CC)C.C(=O)=O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CCOCC>[CH3:3][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[NH:4][CH:1]=1

Participants

6

Reactant 3

HCID 280Carbon DioxideHCID 8471TriethylamineHCID 11054368HCID 11054368, compound

Product 1

HCID 6736SkatoleYield 37%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolvent

Procedure

Di(1H,2H,2H-perfluorooctyl)phenylphosphine (80 mg, 0.1 mmol), palladium (II) acetate (11 mg, 0.05 mmol), N-allyl-2-iodoaniline (259 mg, 1 mmol) and triethylamine (0.15 ml, 1.1 mmol) were placed in a 10 ml stainless steel cell. The cell was sealed and pressurised to approximately 5520 kPa (800 psi) (i.e. full of carbon dioxide). The cell was then heated to 100 C. for 64 hrs and then allowed to cool. When the pressure had dropped below 13800 kPa (2000 psi), the cell was vented into ether (100 ml), the cell was opened once atmospheric pressure was reached and washed out with dichloromethane (20 ml). The organic fractions were combined and concentrated in vacuo to give the crude product. The product was purified by flash column chromatography on silica gel, eluting with 20% ether in hexane to give a white crystalline solid (49 mg, 0.37 mmol, 37%); δH (250 MHz; CDCl3) 7.85 (1H, br, NH), 7.63 (1H, m, H7), 7.34 (1H, m, H4), 7.15-7.26 (2H, m, H5 and H6), 6.97 (1H, s, NHCH), 2.38 (3H, s, Me).

Workup

  1. customThe cell was sealed
  2. temperatureThe cell was then heated to 100 C
  3. temperatureto cool
  4. additionWhen the pressure had dropped below 13800 kPa (2000 psi)
  5. washwashed out with dichloromethane (20 ml)
  6. concentrationconcentrated in vacuo
  7. customto give the crude product
  8. customThe product was purified by flash column chromatography on silica gel
  9. washeluting with 20% ether in hexane

Sources & evidence

ORD record
ord-cad34c7d6df24590a730fdb800c93627
Source dataset
uspto-grants-2002_10
Patent number
US06458985B1

Reaction notes

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