Thiophenol → 1,1-Dimethylethyl (3S)-3-[(3-chloro-4-cyanophenyl)amino]-4-(methylamino)butanoate

HRID 1160396Notes

Reaction equation

HRID 1160396 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH:10][C@H:11]([CH2:20][N:21]([CH3:34])S(C2C=CC=CC=2[N+]([O-])=O)(=O)=O)[CH2:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH:5]=[CH:6][C:7]=1[C:8]#[N:9].C1(S)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.O>[Cl:1][C:2]1[CH:3]=[C:4]([NH:10][C@H:11]([CH2:20][NH:21][CH3:34])[CH2:12][C:13]([O:15][C:16]([CH3:19])([CH3:17])[CH3:18])=[O:14])[CH:5]=[CH:6][C:7]=1[C:8]#[N:9]

Participants

6

Reactant 3

HCID 7969ThiophenolHCID 11430Potassium CarbonateHCID 595161881,1-Dimethylethyl (3S)-3-[(3-chloro-4-cyanophenyl)amino]-4-{methyl[(2-nitrophenyl)sulfonyl]amino}butanoate

Product 1

HCID 595162571,1-Dimethylethyl (3S)-3-[(3-chloro-4-cyanophenyl)amino]-4-(methylamino)butanoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

The crude 1,1-dimethylethyl (3S)-3-[(3-chloro-4-cyanophenyl)amino]-4-{methyl[(2-nitrophenyl)sulfonyl]amino}butanoate from the previous step (31.8 g), phenyl hydrosulfide (1.5 equiv., 10.32 g, 94 mmol), and K2CO3 (325 mesh, 3 equiv., 25.9 g, 188 mmol) in DMF (100 mL) were stirred at room temperature for 30 min. The reaction mixture was diluted with H2O (300 mL) and extracted with Et2O (4×). The organic extracts were washed with H2O, and 10% aq. Na2CO3, dried, and concentrated to give the titled product which contaminated with the 2-nitrophenyl phenyl sulfide by product (31.7 g). This contaminated product was used directly in the next step.

Workup

  1. extractionextracted with Et2O (4×)
  2. washThe organic extracts were washed with H2O, and 10% aq. Na2CO3
  3. customdried
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-42d7c57a4c0e4a88a8936f780bebd152
Source dataset
uspto-grants-2010_10
Patent number
US07816395B2

Reaction notes

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