Trifluoroacetic acid → N-[4-(2-bromoethyl)phenyl]methanesulfonamide

HRID 466350Notes

Reaction equation

HRID 466350 reaction equation
[Br:1][CH2:2][C:3]([C:5]1[CH:15]=[CH:14][C:8]([NH:9][S:10]([CH3:13])(=[O:12])=[O:11])=[CH:7][CH:6]=1)=O.FC(F)(F)C(O)=O.C([SiH](CC)CC)C>>[Br:1][CH2:2][CH2:3][C:5]1[CH:6]=[CH:7][C:8]([NH:9][S:10]([CH3:13])(=[O:12])=[O:11])=[CH:14][CH:15]=1

Participants

4

Reactant 3

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 15592151N-(4-(2-bromoacetyl)phenyl)methanesulfonamide2×

Product 1

HCID 21182029N-[4-(2-bromoethyl)phenyl]methanesulfonamide

Procedure

According to the method of Doyle and coworkers in C. T. West, et al., J. Org. Chem. 38, 2675 (1973), a stirred mixture of 4'-(2-bromoacetyl)methanesulfonanilide as prepared in Preparation 4 (6.0 g, 0.021 mol), trifluoroacetic acid (32.7 g, 0.287 mol) and triethylsilane (10.5 g, 0.0902 mol), under N2, is refluxed for 2.5 days and concentrated in vacuo. The residue is mixed with toluene, concentrated, dissolved in 1N NaOH and washed with Et2O. The aqueous layer is acidified with HCl to pH 2 and extracted well with Et2O. The combined organic extracts are dried (MgSO4) and concentrated in vacuo. The residue is chromatographed on silica gel (300 g) with 1.5% MeOH:CH2Cl2 and N-[4-(2-bromoethyl)phenyl]methanesulfonamide is crystallized from EtOAc:SSB, mp: 92°-94° C.

Workup

  1. temperatureis refluxed for 2.5 days
  2. concentrationconcentrated in vacuo
  3. additionThe residue is mixed with toluene
  4. concentrationconcentrated
  5. dissolutiondissolved in 1N NaOH
  6. washwashed with Et2O
  7. extractionextracted well with Et2O
  8. dry with materialThe combined organic extracts are dried (MgSO4)
  9. concentrationconcentrated in vacuo
  10. customThe residue is chromatographed on silica gel (300 g) with 1.5% MeOH
  11. customCH2Cl2 and N-[4-(2-bromoethyl)phenyl]methanesulfonamide is crystallized from EtOAc

Sources & evidence

ORD record
ord-8adb116b070d4a2493515e2097c8bfc3
Source dataset
uspto-grants-1992_10
Patent number
US05155268

Reaction notes

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