Ethyl Acetate → 7-Bromo-5-methyl-5-thien-2-yl-1,2,3,5-tetrahydro-4,1-benzoxazepine

HRID 1816901Notes

Reaction equation

HRID 1816901 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=O)[CH2:9][O:8][C:7]([CH3:18])([C:13]3[S:14][CH:15]=[CH:16][CH:17]=3)[C:6]=2[CH:19]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[NH4+].C(OCC)(=O)C>C1COCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][CH2:10][CH2:9][O:8][C:7]([CH3:18])([C:13]3[S:14][CH:15]=[CH:16][CH:17]=3)[C:6]=2[CH:19]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 21226445Aluminium lithium hydrideHCID 688661097-Bromo-5-methyl-5-thien-2-yl-1,5-dihydro-4,1-benzoxazepin-2(3H)-one

Product 1

HCID 688643127-Bromo-5-methyl-5-thien-2-yl-1,2,3,5-tetrahydro-4,1-benzoxazepineYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 7-bromo-5-methyl-5-thien-2-yl-1,5-dihydro-4,1-benzoxazepin-2(3H)-one (5 g, 14.6 mmol) in anhydrous THF (100 mL) was added lithium aluminum hydride (0.2 g, 5.2 mmol) at rt under nitrogen. After addition, the mixture was stirred for 3 hrs and treated with aqueous ammonium chloride solution (200 mL). Ethyl acetate (300 mL) was added. Organic layer was separated, dried (MgSO4), and concentrated to afford 7-bromo-5-methyl-5-thien-2-yl-1,2,3,5-tetrahydro-4,1-benzoxazepine as an oil (4 g, 85%). A white solid as a HCl salt: 1H NMR (DMSO-d6): δ 7.52 (dd, J=5.0, 0.8 Hz, 1H), 7.31 (dd, J=8.5, 2.1 Hz, 1H), 7.12 (d, J=2.1 Hz, 1H), 6.95-7.04 (m, 2H), 6.78 (dd, J=3.5, 0.9 Hz, 1H), 3.61-3.85 (m, 4H), 3.12 (m, 2H), 2.93 (s, 3H); MS (ESI) m/z 324/326 ({M+H]+); Anal. calcd for C14H14BrNOS HCl: C, 46.62; H, 4.19; N, 3.88. Found: C, 46.70; H, 3.99; N, 3.83.

Workup

  1. additionAfter addition
  2. customOrganic layer was separated
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-1bf1a7214c8c4998afe54d1e0faa406a
Source dataset
uspto-grants-2009_10
Patent number
US07598237B2

Reaction notes

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