Sodium Thiosulfate → tert-butyl (2S)-7-bromo-2-methyl-8-(1-methylethyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate

HRID 1404995Notes

Reaction equation

HRID 1404995 reaction equation
[CH3:1][C@H:2]1[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:6][C:5]2[S:16][CH:17]=[C:18]([CH:19]([CH3:21])[CH3:20])[C:4]=2[O:3]1.[Br:22]N1C(=O)CCC1=O.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C>[Br:22][C:17]1[S:16][C:5]2[CH2:6][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:13])[CH3:14])=[O:10])[CH2:8][C@H:2]([CH3:1])[O:3][C:4]=2[C:18]=1[CH:19]([CH3:21])[CH3:20]

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 67184N-bromobutanimideHCID 86668493tert-butyl (2S)-2-methyl-8-(1-methylethyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate

Product 1

HCID 86668492tert-butyl (2S)-7-bromo-2-methyl-8-(1-methylethyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylateYield 86.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of tert-butyl (2S)-2-methyl-8-(1-methylethyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate (839 mg) obtained in Example 15, step 1, N-bromosuccinimide (503 mg) and acetonitrile (10 mL) was stirred at room temperature for 1.5 hr, 10% aqueous sodium thiosulfate solution was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 3→7% ethyl acetate/hexane) to give the title compound (908 mg, 86%) as a solid.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customthe solvent was evaporated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (solvent gradient; 3→7% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-19ee1e556eda4e1482be5fad96fbe426
Source dataset
uspto-grants-2014_12
Patent number
US08916549B2

Reaction notes

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