Aluminium lithium hydride → 7-methyl-3-phenyl-2,3-dihydro-4H-1,4-benzoxazin-4-amine

HRID 2415820Notes

Reaction equation

HRID 2415820 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][C:8]1[CH:25]=[CH:24][C:11]2[N:12]([N:22]=O)[CH:13]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH2:14][O:15][C:10]=2[CH:9]=1>C(OCC)C.C1COCC1.CCCCCC>[CH3:7][C:8]1[CH:25]=[CH:24][C:11]2[N:12]([NH2:22])[CH:13]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH2:14][O:15][C:10]=2[CH:9]=1

Participants

6

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 223363397-methyl4-nitroso-3-phenyl-3,4-dihydro-2H-1,4-benzoxazine

Product 1

HCID 223363427-methyl-3-phenyl-2,3-dihydro-4H-1,4-benzoxazin-4-amineYield 75.2%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A slurry of lithium aluminum hydride (6.9 g, 183 mmol) in ethyl ether (300 mL) is stirred in an ice bath under an argon atmosphere. A solution of 7-methyl-4-nitroso-3-phenyl-3,4-dihydro-2H-1,4-benzoxazine (23.22 g, 91.3 mmol) in ethyl ether (250 mL) and dry THF (40 mL) is added dropwise over 1.5 h. The mixture is removed from the ice bath and allowed to stir for 18 h. Water (50 mL) is slowly added, forming solids. The solids are collected by filtration and washed with ethyl ether. The resulting filtrates are combined and washed three times with water (400 mL), dried over magnesium sulfate, and concentrated to dryness to give a solid. The solids are slurried in hexane, collected, and dried to give 16.5 g (69%) of 7-methyl-3-phenyl-2,3-dihydro-4H-1,4-benzoxazin-4-amine.

Workup

  1. customThe mixture is removed from the ice bath
  2. additionWater (50 mL) is slowly added
  3. customforming solids
  4. filtrationThe solids are collected by filtration
  5. washwashed with ethyl ether
  6. washwashed three times with water (400 mL)
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated to dryness
  9. customto give a solid
  10. customcollected
  11. customdried

Sources & evidence

ORD record
ord-80a4ac9b6d774dfd9f4284e41a636694
Source dataset
uspto-grants-2004_11
Patent number
US06821970B2

Reaction notes

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