Triethylamine → Tert-butyl 4-bromo-5-oxoazepane-1-carboxylate

HRID 1487951Notes

Reaction equation

HRID 1487951 reaction equation
[O:1]=[C:2]1[CH2:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:4][CH2:3]1.[Br:16]Br.C(N(CC)CC)C.CC(OC(OC(OC(C)(C)C)=O)=O)(C)C>C(Cl)(Cl)Cl>[Br:16][CH:8]1[C:2](=[O:1])[CH2:3][CH2:4][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:6][CH2:7]1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 24408BromineHCID 90495Di-tert-butyl dicarbonateHCID 1512679N-Boc-hexahydro-1H-azepin-4-one2×

Product 1

HCID 59143774Tert-butyl 4-bromo-5-oxoazepane-1-carboxylateYield 27%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

To a solution tert-butyl 4-oxoazepane-1-carboxylate (compound 82.2, 11.0 g, 51.6 mmol) in chloroform (220 mL) at 0° C. was added drop-wise a solution of bromine (3.98 mL, 77.6 mmol) in chloroform (110 mL). The resulting mixture was stirred at room temperature overnight, then the solids that formed were collected by filtration and dissolved in dichloromethane (200 mL). Triethylamine (16.8 mL, 121 mmol) and (Boc)2O (8.70 g, 40.3 mmol) were added to the mixture at 0° C. and the resulting solution was stirred for 3 h at room temperature, and then concentrated under reduced pressure. The crude residue was purified by silica gel chromatography using ethyl acetate/petroleum ether (1:10) as the eluent to give 4.0 g (27%) of the title compound as a yellow oil.

Workup

  1. customthe solids that formed
  2. filtrationwere collected by filtration
  3. dissolutiondissolved in dichloromethane (200 mL)
  4. stirringthe resulting solution was stirred for 3 h at room temperature
  5. concentrationconcentrated under reduced pressure
  6. customThe crude residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-fffbe8dbe9284d598c9f637c8e2e35ca
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

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