Methyl iodide → 7-amino-4-methyl-2H-1,4-benzoxazine

HRID 2102950Notes

Reaction equation

HRID 2102950 reaction equation
[C:1](=O)([O-])[O-].[K+].[K+].CI.[N+:9]([C:12]1[CH:13]=[CH:14][C:15]2[NH:20][CH2:19][CH2:18][O:17][C:16]=2[CH:21]=1)([O-])=O.[H-].[Na+]>CN(C=O)C>[CH3:1][N:20]1[CH2:19][CH2:18][O:17][C:16]2[CH:21]=[C:12]([NH2:9])[CH:13]=[CH:14][C:15]1=2

Participants

6

Reactant 4

HCID 6328Methyl iodide2×HCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 184161517-Nitro-3,4-dihydro-2H-1,4-benzoxazine

Product 1

HCID 112174297-amino-4-methyl-2H-1,4-benzoxazineYield 95.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Potassium carbonate (800 mg, 6 mmol) and methyl iodide (1.3 g, 9 mmol) were added to a solution of 3,4-dihydro-7-nitro-2H-benzo[b][1,4]oxazine (540 mg, 3 mmol) in DMF (10 mL). The reaction mixture was stirred at room temperature overnight. Sodium hydride (100 mg, 95%) and methyl iodide (1.0 g) were added and the reaction mixture was stirred at room temperature overnight. The solvent was removed under vacuum and the residue was suspended in water. A solid precipitated which was filtered and washed with water. The bright yellow solid was then suspended in MeOH (20 mL) and Pd/C (10%) was added. The suspension was stirred under an atmosphere of hydrogen overnight, then filtered through Celite® and the filtrate concentrated under vacuum to give the product (470 mg) as a purple oil.

Workup

  1. stirringthe reaction mixture was stirred at room temperature overnight
  2. customThe solvent was removed under vacuum
  3. customA solid precipitated which
  4. filtrationwas filtered
  5. washwashed with water
  6. additionPd/C (10%) was added
  7. stirringThe suspension was stirred under an atmosphere of hydrogen overnight
  8. filtrationfiltered through Celite®
  9. concentrationthe filtrate concentrated under vacuum

Sources & evidence

ORD record
ord-df0d2d41dcc2494e99b7aa2d7fb336cd
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

Loading…