HCID 59281523, compound → 6-Bromo-3,4-dihydro-5-methyl-2H-1,4-benzoxazine

HRID 1912608Notes

Reaction equation

HRID 1912608 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][C:8](=O)[NH:7][C:6]=2[C:12]=1[CH3:13]>O1CCCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][CH2:8][NH:7][C:6]=2[C:12]=1[CH3:13]

Participants

3

Reactant 1

HCID 59281523HCID 59281523, compound

Product 1

HCID 595786626-Bromo-3,4-dihydro-5-methyl-2H-1,4-benzoxazine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

An ice cold mixture of 6-bromo-5-methyl-2H-1,4-benzoxazin-3(4H)-one (3.05 g, 12.59 mmol) in tetrahydrofuran (THF) (40 mL) was treated with borane tetrahydrofuran complex (1.0 M solution in tetrahydrofuran (18.88 mL, 18.88 mmol) and the mixture was stirred at ambient temperature for 150 minutes. The mixture was cooled to 0° C. and then quenched slowly with 1N NaOH (30 mL). The mixture was extracted with ethyl acetate, then washed with 1N NaOH, dried over sodium sulfate, filtered and then concentrated to a thick dark brown oil. The material was purified on silica gel (95:4:1 dichloromethane/methanol/ammonium hydroxide, gradient) to afford an off-white solid: 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 6.87 (d, J=8.6 Hz, 1 H), 6.57 (d, J=8.8 Hz, 1 H), 4.31-4.15 (m, 2 H), 3.56-3.38 (m, 2 H), 2.22 (s, 3 H); LC/MS (m/z) ES+=228 (M+1).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. customquenched slowly with 1N NaOH (30 mL)
  3. extractionThe mixture was extracted with ethyl acetate
  4. washwashed with 1N NaOH
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated to a thick dark brown oil
  8. customThe material was purified on silica gel (95:4:1 dichloromethane/methanol/ammonium hydroxide, gradient)
  9. customto afford an off-white solid

Sources & evidence

ORD record
ord-b8f1e14531f940b28ab81ba3399cdad7
Source dataset
uspto-grants-2013_12
Patent number
US08609653B2

Reaction notes

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