Sodium Iodide → (R)-4-allyl-7-benzyloxy-3-(4-benzyloxyphenyl)-3,4-dihydro-2H-benzo[1,4]oxazine

HRID 460462Notes

Reaction equation

HRID 460462 reaction equation
[CH2:1]([O:8][C:9]1[CH:32]=[CH:31][C:12]2[NH:13][C@H:14]([C:17]3[CH:22]=[CH:21][C:20]([O:23][CH2:24][C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)=[CH:19][CH:18]=3)[CH2:15][O:16][C:11]=2[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[I-].[Na+].C(=O)([O-])[O-].[K+].[K+].[CH2:41](Br)[CH:42]=[CH2:43]>CC(C)=O.C(OCC)(=O)C.CCCCCC.O>[CH2:43]([N:13]1[C:12]2[CH:31]=[CH:32][C:9]([O:8][CH2:1][C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=3)=[CH:10][C:11]=2[O:16][CH2:15][C@H:14]1[C:17]1[CH:22]=[CH:21][C:20]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)=[CH:19][CH:18]=1)[CH:42]=[CH2:41]

Participants

8

Reactant 4

HCID 5238Sodium IodideHCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 20726824(R)-7-benzyloxy-3-(4-benzyloxyphenyl)-3,4-dihydro-2H-benzo[1,4]oxazine

Product 1

HCID 20726823(R)-4-allyl-7-benzyloxy-3-(4-benzyloxyphenyl)-3,4-dihydro-2H-benzo[1,4]oxazineYield 85%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of (R)-7-benzyloxy-3-(4-benzyloxyphenyl)-3,4-dihydro-2H-benzo[1,4]oxazine (47.6 mg, 0.112 mmol), sodium iodide (67 mg, 0.450 mmol), potassium carbonate (31 mg, 0.224 mmol) and allyl bromide (0.04 ml, 0.473 mmol) in acetone (1 ml) was stirred for 3 hours at 50° C. under a nitrogen stream and then heated under reflux for 7 hours. After cooling, water was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/5, v/v) to give (R)-4-allyl-7-benzyloxy-3-(4-benzyloxyphenyl)-3,4-dihydro-2H-benzo[1,4]oxazine (44 mg, Yield 85%).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 7 hours
  3. temperatureAfter cooling
  4. extractionwas then extracted with ethyl acetate
  5. washThe organic layer was washed with saturated aqueous sodium chloride
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue was purified by silica gel column chromatography (eluent

Sources & evidence

ORD record
ord-c9fcdc313af04cbb8cb4a4a78be44d09
Source dataset
uspto-grants-2007_03
Patent number
US07196081B2

Reaction notes

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