Oxygen → HCID 11697437, compound

HRID 747561Notes

Reaction equation

HRID 747561 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[NH:9][C:10](=[O:28])[O:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27].O=O.[C:31](=O)([O-:33])[O-:32].[K+].[K+]>O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:12]([O:11][C:10]([NH:9][C:3]1[CH:4]=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[C:31]([OH:33])=[O:32])=[O:28])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

7

Reactant 3

HCID 977OxygenHCID 11430Potassium CarbonateHCID 11698173HCID 11698173, compound

Product 1

HCID 11697437HCID 11697437, compoundYield 77.2%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
115 °C

Procedure

217.5 g (478.5 mmol) of hexadecyl (2-bromo-4-methylphenyl)carbamate, 0.5 g (0.7 mmol) of bis(triphenylphosphine)palladium dichloride and 2.5 g (9.3 mmol) of triphenylphosphine were introduced into an autoclave. The autoclave was closed, flushed with nitrogen and an oxygen-free solution of 78.1 g (565.3 mmol) of potassium carbonate in 400 ml of water is added. The autoclave is evacuated and then 2 bar of carbon monoxide are injected and heated to 115° C. The pressure is subsequently adjusted to 8 bar. After CO uptake ceases, the mixture is cooled to RT and 200 ml of toluene are added. The pH is adjusted to 2 with 2M aqueous HCl solution, and the organic phase is separated off. The aqueous phase is extracted anew with 100 ml of toluene, the organic phase is separated off, and the two toluene extracts are combined. Removal of the solvent in vacuo results in 154.9 g (369.2 mmol, 77%) of 2-hexadecyloxycarbonylamino-5-methylbenzoic acid in the form of a pale yellow-coloured solid.

Workup

  1. customThe autoclave was closed
  2. customflushed with nitrogen
  3. customThe autoclave is evacuated
  4. temperatureAfter CO uptake ceases, the mixture is cooled to RT
  5. addition200 ml of toluene are added
  6. customthe organic phase is separated off
  7. extractionThe aqueous phase is extracted anew with 100 ml of toluene
  8. customthe organic phase is separated off
  9. customRemoval of the solvent in vacuo

Sources & evidence

ORD record
ord-4b3b30f974a14dc58b0689002fa895bb
Source dataset
uspto-grants-2008_07
Patent number
US07396952B2

Reaction notes

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