Boron tribromide → (E)-5-amino-7'-bromo-4'-fluoro-6,7-dihydro-2H-spiro[[1,4]oxazepine-3,9'-xanthen]-2'-ol

HRID 529400Notes

Reaction equation

HRID 529400 reaction equation
[Br:1][C:2]1[CH:15]=[C:14]2[C:5]([O:6][C:7]3[C:8]([F:25])=[CH:9][C:10]([O:23]C)=[CH:11][C:12]=3[C:13]32[CH2:16][O:17][CH2:18][CH2:19][C:20]([NH2:22])=[N:21]3)=[CH:4][CH:3]=1.B(Br)(Br)Br.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[NH2:22][C:20]1=[N:21][C:13]2([CH2:16][O:17][CH2:18][CH2:19]1)[C:12]1[CH:11]=[C:10]([OH:23])[CH:9]=[C:8]([F:25])[C:7]=1[O:6][C:5]1[C:14]2=[CH:15][C:2]([Br:1])=[CH:3][CH:4]=1

Participants

5

Reactant 3

HCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 68279914(E)-7'-bromo-4'-fluoro-2'-methoxy-6,7-dihydro-2H-spiro[[1,4]oxazepine-3,9'-xanthen]-5-amine

Product 1

HCID 68279594(E)-5-amino-7'-bromo-4'-fluoro-6,7-dihydro-2H-spiro[[1,4]oxazepine-3,9'-xanthen]-2'-ol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (E)-7′-bromo-4′-fluoro-2′-methoxy-6,7-dihydro-2H-spiro[[1,4]oxazepine-3,9′-xanthen]-5-amine (0.990 g, 2.431 mmol) in DCM (24.31 mL) was cooled in an ice-bath for 5 min. Boron tribromide (0.919 mL, 9.72 mmol) was added dropwise to give a resulting brown mixture. The mixture was stirred for 1 h, at which time a saturated aq. sodium bicarbonate solution (25 mL) was added. The mixture was stirred for 5 min. and concentrated on a rotary evaporator to remove the DCM. The mixture was heated with a heat gun for 5 min, and at this point the solid was scraped from the sides of the flask. The flask was sonicated for 1 min, then reheated for 2 min. The flask was again sonicated for 1 min, then cooled to RT. The solid was filtered. The filter cake was washed twice with water, then air-dried under a stream of N2 (g) for 1.5 h to give (E)-5-amino-7′-bromo-4′-fluoro-6,7-dihydro-2H-spiro[[1,4]oxazepine-3,9′-xanthen]-2′-ol as a light-yellow solid. The solid was used without further purification.

Workup

  1. customto give a resulting brown mixture
  2. additionwas added
  3. concentrationconcentrated on a rotary evaporator
  4. customto remove the DCM
  5. temperatureThe mixture was heated with a heat gun for 5 min
  6. customThe flask was sonicated for 1 min
  7. waitreheated for 2 min
  8. customThe flask was again sonicated for 1 min
  9. filtrationThe solid was filtered
  10. washThe filter cake was washed twice with water
  11. dry with materialair-dried under a stream of N2 (g) for 1.5 h

Sources & evidence

ORD record
ord-e377021e77924aacbf10d7e7abba4c35
Source dataset
uspto-grants-2016_05
Patent number
US09346827B2

Reaction notes

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