Thiophenol → HCID 67336266, compound

HRID 1670544Notes

Reaction equation

HRID 1670544 reaction equation
[H-].[Na+].[C:3]1([SH:9])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[C:10]([O:14][C:15]([N:17]1[CH2:23][CH2:22][C:21]2[C:24]([CH2:29]Cl)=[C:25]([Cl:28])[CH:26]=[CH:27][C:20]=2[CH2:19][CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]>CN(C=O)C.[I-].[K+]>[C:10]([O:14][C:15]([N:17]1[CH2:23][CH2:22][C:21]2[C:24]([CH2:29][S:9][C:3]3[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=3)=[C:25]([Cl:28])[CH:26]=[CH:27][C:20]=2[CH2:19][CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]

Participants

6

Reactant 3

HCID 7969ThiophenolHCID 24758Sodium hydrideHCID 597874103-tert-Butoxycarbonyl-7-chloro-6-chloromethyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine

Product 1

HCID 67336266HCID 67336266, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 4875Potassium IodideCatalystHCID 6228DimethylformamideSolvent2×

Procedure

Add sodium hydride (25 mg, 0.62 mmol, 60% dispersion in mineral oil) to benzenethiol (0.06 mL, 0.51 mmol) in anhydrous DMF (2 mL). Stir the mixture under nitrogen for 5 min and then add 3-tert-butoxycarbonyl-7-chloro-6-chloromethyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine (198 mg, 0.51 mmol) in anhydrous DMF (2 mL) followed by catalytic potassium iodide (1 mg). Stir the reaction at 45° C. for 12 h then cool to room temperature and partition between EtOAc/water. Wash the organic phase with brine. Dry the organic phase over MgSO4, filter and concentrate in vacuo to give a yellow oil. Purify the crude mixture by chromatography on silica gel eluting with hexane/EtOAc (9:1) to give 3-tert-butoxycarbonyl-7-chloro-6-phenylthiomethyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a yellow oil (200 mg, 98%).

Workup

  1. stirringStir
  2. customthe reaction at 45° C. for 12 h
  3. custompartition between EtOAc/water
  4. washWash the organic phase with brine
  5. dry with materialDry the organic phase over MgSO4
  6. filtrationfilter
  7. concentrationconcentrate in vacuo
  8. customto give a yellow oil
  9. customPurify the crude mixture by chromatography on silica gel eluting with hexane/EtOAc (9:1)

Sources & evidence

ORD record
ord-2280aa2517ab4ae5ba403061e89903da
Source dataset
uspto-grants-2011_08
Patent number
US07994163B2

Reaction notes

Loading…