Benzyl mercaptan → 1-Benzylsulfanyl-3-bromo-5-fluoro-2-methoxy-benzene

HRID 389652Notes

Reaction equation

HRID 389652 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4]([Br:9])[C:3]=1[O:10][CH3:11].[C:12]1([CH2:18][SH:19])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.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.CCN(C(C)C)C(C)C>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]>[CH2:18]([S:19][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4]([Br:9])[C:3]=1[O:10][CH3:11])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 7509Benzyl mercaptanHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 27739651,3-Dibromo-5-fluoro-2-methoxybenzene

Product 1

HCID 669111041-Benzylsulfanyl-3-bromo-5-fluoro-2-methoxy-benzene

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

1,3-Dibromo-5-fluoro-2-methoxy-benzene (14.2 g, 50 mmol), phenyl-methanethiol (5.86 ml, 50 mmol), Pd2dba3 (1.145 g, 1.25 mmol, 2.5 mol-%), Xantphos (1.447 g, 2.5 mmol, 5 mol-%) and DIPEA (17.5 ml, 100 mmol) were dissolved in 130 ml dry, degassed 1,4-dioxane and heated to reflux for 3 h. After cooling down the mixture was filtrated and evaporated. The remaining solid (22 g) is chromatographed on silica gel using n-heptane-MTBE as eluent. Yield: 12.42 g, 76%.

Workup

  1. customdry
  2. customdegassed 1,4-dioxane
  3. temperatureheated
  4. temperatureto reflux for 3 h
  5. temperatureAfter cooling down the mixture
  6. filtrationwas filtrated
  7. customevaporated
  8. customThe remaining solid (22 g) is chromatographed on silica gel

Sources & evidence

ORD record
ord-2644cbe5818049a7b54ec3ec3f50d5bf
Source dataset
uspto-grants-2013_02
Patent number
US08378092B2

Reaction notes

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