4-Bromotoluene → HCID 86599156, compound

HRID 2116075Notes

Reaction equation

HRID 2116075 reaction equation
[NH:1]([C:8]1[C:16]2[O:15][CH:14]([CH2:17][O:18][S:19]([C:22]3[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=3)(=[O:21])=[O:20])[CH2:13][C:12]=2[CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:30]1C=CC(C)=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:28][C:25]1[CH:26]=[CH:27][C:22]([S:19]([O:18][CH2:17][CH:14]2[CH2:13][C:12]3[CH:11]=[CH:10][CH:9]=[C:8]([NH:1][C:2]4[CH:7]=[CH:6][C:5]([CH3:30])=[CH:4][CH:3]=4)[C:16]=3[O:15]2)(=[O:21])=[O:20])=[CH:23][CH:24]=1

Participants

6

Reactant 3

HCID 78054-BromotolueneHCID 23676156Sodium t-butoxideHCID 86599157HCID 86599157, compound

Product 1

HCID 86599156HCID 86599156, compoundYield 29.3%

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 1140TolueneSolvent

Procedure

Treatment of (±)-(7-anilino-2,3-dihydro-1-benzofuran-2-yl)methyl-4-methylbenzenesulfonate (0.96 g, 3.0 mmol) in toluene (20 mL) with 1-bromo-4-methylbenzene (0.513 g, 3.0 mmol)dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II)dichloromethane (0.061 g, 0.075 mmol), 1,1′-bis(diphenylphosphino)ferrocene (0.125 g, 0.225 mmol), sodium tert-butoxide (0.18 g, 1.875 mmol) the reaction was allowed to reflux 3 h. The solvent was removed in vacuo. The residue was washed with water (100 mL) and ethyl acetate (50 mL). The combined organic layers were washed with saturated aqueous sodium chloride, dried (magnesium sulfate), and the solvent removed in vacuo to provide a crude oil. Purification by flash column chromatography (silica, ethyl acetate:hexanes 3:10) afforded 0.36 g (29%) of (±)-{7-[(4-methylphenyl)amino]-2,3-dihydro-1-benzofuran-2-yl}methyl 4-methylbenzenesulfonate as a yellow solid. mp 118-120° C.

Workup

  1. temperatureto reflux 3 h
  2. customThe solvent was removed in vacuo
  3. washThe residue was washed with water (100 mL) and ethyl acetate (50 mL)
  4. washThe combined organic layers were washed with saturated aqueous sodium chloride
  5. dry with materialdried (magnesium sulfate)
  6. customthe solvent removed in vacuo
  7. customto provide a crude oil
  8. customPurification by flash column chromatography (silica, ethyl acetate:hexanes 3:10)

Sources & evidence

ORD record
ord-006b7f99d0b54ab48f0854eed6e1059f
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Reaction notes

Loading…