Triphenylphosphine → HCID 57541257, compound

HRID 421734Notes

Reaction equation

HRID 421734 reaction equation
[CH3:1][N:2]([CH3:11])[S:3]([CH2:6][C:7]([O:9][CH3:10])=[O:8])(=[O:5])=[O:4].[H-].[Na+].Br[C:15]1[CH:16]=[CH:17][C:18]2[CH:29]=[CH:28][C:22]3=[N:23][CH:24]=[C:25]([Cl:27])[CH:26]=[C:21]3[C:20](=[O:30])[C:19]=2[CH:31]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[Cl:27][C:25]1[CH:26]=[C:21]2[C:20](=[O:30])[C:19]3[CH:31]=[C:15]([CH:6]([S:3]([N:2]([CH3:11])[CH3:1])(=[O:4])=[O:5])[C:7]([O:9][CH3:10])=[O:8])[CH:16]=[CH:17][C:18]=3[CH:29]=[CH:28][C:22]2=[N:23][CH:24]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 159808187-Bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-B]pyridin-5-oneHCID 57541258HCID 57541258, compound

Product 1

HCID 57541257HCID 57541257, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

A 200 mL round bottom flask was charged with methyl [(dimethylamino)sulfonyl]acetate (5.26 g, 29.0 mmol) and dioxane (77 ml), cooled to 0° C. and then sodium hydride (2.321 g, 58.0 mmol) was added in one portion. After 15 min., the mixture was warmed to room temperature and 7-bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-b]pyridin-5-one (6.20 g, 19.34 mmol) was added followed by Pd2(dba)3 (0.708 g, 0.774 mmol) and triphenylphosphine (1.217 g, 4.64 mmol). The resulting suspension was degassed by sparging with nitrogen for 30 min. Then, the mixture was heated to 70° C. and left to stir overnight. The reaction was then cooled to room temperature, poured into brine (500 mL) and extracted with dichloromethane (3×150 mL). The combined organics were then dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient) to afford the title compound as a yellow oil that solidified to a yellow solid upon standing. 1H NMR (600 MHz, DMSO-D6) δ 9.00 (d, 1H); 8.49 (d, 1H); 8.47 (d, 1H); 8.07 (dd, 1H); 7.88 (d, 1H); 7.48 (d, 1H); 7.34 (d, 1H); 6.05 (s, 1H); 3.75 (s, 3H); 2.68 (s, 6H). LRMS (APCI) calculated for C19H18ClN2O5S [M+H]+, 421.1; found 421.0.

Workup

  1. temperaturethe mixture was warmed to room temperature
  2. customThe resulting suspension was degassed
  3. customby sparging with nitrogen for 30 min
  4. temperatureThen, the mixture was heated to 70° C.
  5. waitleft
  6. temperatureThe reaction was then cooled to room temperature
  7. additionpoured into brine (500 mL)
  8. extractionextracted with dichloromethane (3×150 mL)
  9. dry with materialThe combined organics were then dried over anhydrous Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient)

Sources & evidence

ORD record
ord-a402aa9192bc4e99aa342f62f245d70e
Source dataset
uspto-grants-2012_01
Patent number
US08101603B2

Reaction notes

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