Stannanecarbonitrile, tributyl- → 2-Oxindole-6-carbonitrile

HRID 1387420Notes

Reaction equation

HRID 1387420 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7](=[O:11])[NH:8]2)=[CH:4][CH:3]=1.C([Sn]([C:25]#[N:26])(CCCC)CCCC)CCC.O.[Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[Cl-].[Cl-].[Cl-]>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.ClC(Cl)C>[C:25]([C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7](=[O:11])[NH:8]2)=[CH:4][CH:3]=1)#[N:26]

Participants

6

Reactant 3

HCID 200512Stannanecarbonitrile, tributyl-HCID 27732896-bromo-2,3-dihydro-1H-indol-2-oneHCID 86757223HCID 86757223, compound

Product 1

HCID 27733482-Oxindole-6-carbonitrileYield 30.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 63651,1-DichloroethaneSolvent

Procedure

6-Bromo-1,3-dihydro-indol-2-one (0.621 g, 2.93 mmol), tributyltin cyanide 1.11 g, 3.5 mmol), tetraammonium chloride hydrate (0.97 g, 5.9 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.21 g, 0.3 mmol) and tetrakis (triphenylphosphine)palladium(0) (0.342 g, 0.3 mmol) were treated with dichloroethane (100 mL) and the reaction refluxed for 16 h under nitrogen with stirring. A further addition of tetrakis (triphenylphosphine)palladium(0) (0.23 g, 0.2 mmol) was made and reflux continued a further 6 h. A third addition of tetrakis (triphenylphosphine)palladium(0) (0.345 9, 0.3 mmol) was made and the reaction returned to reflux for 16 h. On cooling the reaction solution was washed twice with an aqueous solution of potassium fluoride (50 mL) and the organic phase dried over magnesium sulfate, filtered and evaporated to dryness. The product was subjected to chromatography on silica gel using dichloromethane to give 140 mg of 6-cyano-1,3-dihydro-indol-2-one contaminated with triphenylphosphine oxide. A second chromatographic purification chromatography on silica gel using dichloromethane gave 61 mg of pure 6-cyano-1,3-dihydro-indol-2-one; 1H-NMR (DMSO-d6): δ10.64 (bs, 1H), 7.37 (s, 2H), 7.10 (s, 1H), 3.56 (s, 2H). Mass spectrum (negative ion electrospray): m/z=157 (M−1, 100%).

Workup

  1. temperaturethe reaction refluxed for 16 h under nitrogen
  2. temperaturereflux
  3. temperatureto reflux for 16 h
  4. temperatureOn cooling the reaction solution
  5. washwas washed twice with an aqueous solution of potassium fluoride (50 mL)
  6. dry with materialthe organic phase dried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated to dryness

Sources & evidence

ORD record
ord-29591e42a1d84f6b929a08cb866091fd
Source dataset
uspto-grants-2001_07
Patent number
US06268391B1

Reaction notes

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