Triphenylphosphine → 794521-56-5

HRID 1751970Notes

Reaction equation

HRID 1751970 reaction equation
Cl[S:2]([C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[NH:10][C:9](=[O:14])[CH2:8]2)(=O)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[SH:2][C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[NH:10][C:9](=[O:14])[CH2:8]2

Participants

4

Reactant 2

HCID 11776TriphenylphosphineHCID 49625062-oxo-2,3-dihydro-1H-indole-5-sulfonyl chloride

Product 1

HCID 11983903794521-56-5

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

The 5-chlorosulfonyl oxindole from the previous step, 42.23 g (182.3 mmol) was suspended in anhydrous dichloromethane (100 mL) in a 1 L round flask. The mixture was cooled on ice slush bath and a solution of triphenylphosphine 167.5 g (638 mmol, 3.5 eq.) in anhydrous dichloromethane (300 mL) was dropwise added from an addition funnel under nitrogen with cooling over a 45 min period. After complete addition the flask was removed from the cooling bath and the mixture was stirred at room temperature for 3 hours. The reaction was quenched by water addition, 200 mL. The flask with the biphasic mixture was placed on a 50° C. water bath and the mixture was refluxed under nitrogen for 1 hour, then cooled on ice. The precipitated product was collected by filtration, washed thoroughly with ice-chilled dichloromethane and ice water, then dried by suction and on highvac, to provide 19.58 g of a pure product. The biphasic filtrates were de-oxygenated by argon/vacuum purge (3 times). The mixture was made strongly alkaline by addition of 50% aq. NaOH solution, shaken under Ar and then rapidly separated. The organic phase was re-extracted with water. The aqueous phases were promptly washed with fresh dichloromethane (200 mL). The combined aqueous extracts were made acidic by addition of 6M HCl, the mixture was cooled on ice, the precipitated product was collected by filtration, washed with ice-cold water, dried by suction and on highvac, to provide a second crop of the product, 7.15 g. The combined yield was 26.73 g (88.5% th) of a light tan solid. 1H-NMR (d6-DMSO, 400 MHz): 10.339 (s, 1H), 7.151 (s, 1H), 7.108 (m, 1H), 6.707 (d, 8.0 Hz, 1H), 5.109 (s, 1H), 3.436 (s, 2H)

Workup

  1. temperatureThe mixture was cooled on ice slush bath
  2. temperaturewith cooling over a 45 min period
  3. additionAfter complete addition the flask
  4. customwas removed from the cooling bath
  5. customThe reaction was quenched by water addition, 200 mL
  6. customwas placed on a 50° C.
  7. temperaturethe mixture was refluxed under nitrogen for 1 hour
  8. temperaturecooled on ice
  9. filtrationThe precipitated product was collected by filtration
  10. washwashed thoroughly with ice-
  11. temperaturechilled dichloromethane and ice water
  12. customdried by suction

Sources & evidence

ORD record
ord-d4629b005d7a48db80025c597110f4e3
Source dataset
uspto-grants-2015_10
Patent number
US09162981B2

Reaction notes

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