Benzyl mercaptan → HCID 117737202, compound

HRID 1504379Notes

Reaction equation

HRID 1504379 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([F:11])=[C:6]([C:8](=[O:10])[CH3:9])[CH:7]=1.C(N(CC)C(C)C)(C)C.[CH2:21]([SH:28])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>O1CCOCC1.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].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH2:21]([S:28][C:2]1[CH:3]=[CH:4][C:5]([F:11])=[C:6]([C:8](=[O:10])[CH3:9])[CH:7]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

7

Reactant 3

HCID 7509Benzyl mercaptanHCID 81531DiisopropylethylamineHCID 226074761-(5-Bromo-2-fluorophenyl)ethanone

Product 1

HCID 117737202HCID 117737202, compoundYield 100.2%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 1-(5-bromo-2-fluorophenyl)ethanone (Matrix Scientific, 3 g, 13.8 mmol), Xantphos (0.800 g, 1.38 mmol), and N,N-diisopropylethylamine (4.83 mL, 27.6 mmol) in 1,4-dioxane (15 mL) was added Pd2(dba)3 (0.633 g, 0.691 mmol). The vial was sparged with argon, sealed, and stirred at 80° C. for 10 minutes. After 10 minutes, the reaction was cooled to ambient temperature, and benzyl mercaptan (1.70 mL, 14.5 mmol) was added. The reaction was flushed with argon, sealed, and stirred at 80° C. After 45 minutes, the reaction mixture was concentrated, diluted with dichloromethane, and passed through a silica-gel pad, eluting with DCM. The filtrate was concentrated and purified by column chromatography, eluting with 10-60% ethyl acetate in heptane, to provide 1-(5-(benzylthio)-2-fluorophenyl)ethanone (3.6 g, quantative yield) as a yellow oil. m/z (ESI) 261.0 (M+H).

Workup

  1. customThe vial was sparged with argon
  2. customsealed
  3. waitAfter 10 minutes
  4. temperaturethe reaction was cooled to ambient temperature
  5. customThe reaction was flushed with argon
  6. customsealed
  7. stirringstirred at 80° C
  8. waitAfter 45 minutes
  9. concentrationthe reaction mixture was concentrated
  10. additiondiluted with dichloromethane
  11. washeluting with DCM
  12. concentrationThe filtrate was concentrated
  13. custompurified by column chromatography
  14. washeluting with 10-60% ethyl acetate in heptane

Sources & evidence

ORD record
ord-560490f1b59544a99e12d441a643e9c8
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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