4-Methoxy-alpha-toluenethiol → 2,5-Dichloro-1-methoxy-3-((4-methoxybenzyl)sulfanyl)benzene

HRID 591426Notes

Reaction equation

HRID 591426 reaction equation
CCN(C(C)C)C(C)C.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.Br[C:53]1[CH:58]=[C:57]([Cl:59])[CH:56]=[C:55]([O:60][CH3:61])[C:54]=1[Cl:62].[CH3:63][O:64][C:65]1[CH:70]=[CH:69][C:68]([CH2:71][SH:72])=[CH:67][CH:66]=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].O.C1(C)C=CC=CC=1>[Cl:62][C:54]1[C:53]([S:72][CH2:71][C:68]2[CH:69]=[CH:70][C:65]([O:64][CH3:63])=[CH:66][CH:67]=2)=[CH:58][C:57]([Cl:59])=[CH:56][C:55]=1[O:60][CH3:61]

Participants

8

Reactant 4

HCID 804074-Methoxy-alpha-toluenethiolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 577991361-Bromo-2,5-dichloro-3-methoxybenzene

Product 1

HCID 897678422,5-Dichloro-1-methoxy-3-((4-methoxybenzyl)sulfanyl)benzene

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a mixture of DIPEA (5.77 mL), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.488 g), 1-bromo-2,5-dichloro-3-methoxybenzene (4.32 g) and (4-methoxyphenyl)methanethiol (2.47 mL) and toluene (100 mL) was added tris(dibenzylideneacetone)dipalladium (0) (Pd2(dba)3, 0.773 g) at room temperature. The mixture was refluxed for 5 h. After cooling, water was added to the mixture and the mixture was extracted with EtOAc. The organic layer was separated, washed with brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (5.66 g).

Workup

  1. temperatureThe mixture was refluxed for 5 h
  2. temperatureAfter cooling
  3. extractionthe mixture was extracted with EtOAc
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by silica gel column chromatography (EtOAc/hexane)

Sources & evidence

ORD record
ord-e91466d0646d48a0bc5cbfed8a475e07
Source dataset
uspto-grants-2016_01
Patent number
US09238639B2

Reaction notes

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