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

HRID 1279706Notes

Reaction equation

HRID 1279706 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-methyl4-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-97a07b2b69a7413f863f08051db66a7f
Source dataset
uspto-grants-2002_09
Patent number
US06448397B1

Reaction notes

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