2-Pyrrolidone → tert-butyl 9-(2-oxopyrrolidin-1-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

HRID 886951Notes

Reaction equation

HRID 886951 reaction equation
Br[C:2]1[C:12]2[O:11][CH2:10][CH2:9][N:8]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:7][C:6]=2[CH:5]=[CH:4][CH:3]=1.[NH:20]1[CH2:24][CH2:23][CH2:22][C:21]1=[O:25].P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C@@H]1(N)CCCC[C@H]1N>C(OCC)(=O)C.O.O1CCOCC1.CN(C)C=O>[O:25]=[C:21]1[CH2:22][CH2:23][CH2:24][N:20]1[C:2]1[C:12]2[O:11][CH2:10][CH2:9][N:8]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:7][C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 120252-PyrrolidoneHCID 438061,2-Diaminocyclohexane, trans-HCID 62657Potassium Phosphate, TribasicHCID 59403519Tert-butyl 9-bromo-2,3-dihydrobenzo[F][1,4]oxazepine-4(5H)-carboxylate

Product 1

HCID 68580680tert-butyl 9-(2-oxopyrrolidin-1-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylateYield 86.4%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

tert-Butyl 9-bromo-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (328 mg, 1.00 mmol), 2-pyrrolidone (85.1 mg, 1.00 mmol), tripotassium phosphate (318 mg, 1.50 mmol), N,N-dimethylformamide (3 ml), dioxane (3 ml) and 1,2-trans-cyclohexanediamine (0.025 ml) mixture were stirred at room temperature under a nitrogen atmosphere for 5 min. Copper iodide(I) (35.0 mg, 0.184 mmol) was added, and the mixture was stirred at 110° C. under a nitrogen atmosphere for 20 hr. The reaction mixture was poured into water (10 ml) and ethyl acetate (10 ml), and filtered through celite. The organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1) to give the desired product (260 mg, 86.4%) as an oil.

Workup

  1. filtrationfiltered through celite
  2. customThe organic layer was separated
  3. washwashed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1)

Sources & evidence

ORD record
ord-c14052523f5e4f6488e0f37b1d40785e
Source dataset
uspto-grants-2012_08
Patent number
US08247403B2

Reaction notes

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