Hydrochloric Acid → 7-(hydroxymethyl)-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-one

HRID 1929432Notes

Reaction equation

HRID 1929432 reaction equation
[CH3:1][C:2]1([CH3:17])[C:7](=[O:8])[NH:6][C:5]2[CH:9]=[CH:10][C:11]([C:13](OC)=[O:14])=[CH:12][C:4]=2[O:3]1.[H-].C([Al+]CC(C)C)C(C)C.Cl>O1CCCC1.C1(C)C=CC=CC=1.C(=O)=O.CC(C)=O>[OH:14][CH2:13][C:11]1[CH:10]=[CH:9][C:5]2[NH:6][C:7](=[O:8])[C:2]([CH3:17])([CH3:1])[O:3][C:4]=2[CH:12]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 10585820Methyl 3,4-dihydro-2,2-dimethyl-3-oxo-2H-1,4-benzoxazine-7-carboxylateHCID 21225700Diisobutylaluminumhydride2×

Product 1

HCID 667895427-(hydroxymethyl)-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-oneYield 44.2%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolventHCID 18522661Acetone cardiceSolvent

Procedure

To a solution of methyl 2,2-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-7-carboxylate (1.00 g) in tetrahydrofuran (50 mL) was added dropwise 1M diisobutyl aluminum hydride solution in toluene (13.1 mL) under cooling in dry ice/acetone bath under argon atmosphere, and the mixture was stirred at the same temperature for 2.5 hours. Thereto was further added 1M diisobutyl aluminum hydride solution in toluene (8.5 mL), and the mixture was stirred at the same temperature for 1.5 hours. The reaction mixture was poured to an aqueous 2N HCl solution, and the mixture was extracted with diethylether. The organic layer was washed successively with an aqueous saturated sodium hydrogencarbonate solution and brine, dried over sodium sulfate and concentrated in vacuo. The residue was triturated in ethyl acetate to give 7-(hydroxymethyl)-2,2-dimethyl-2H-1,4-benzoxazin-3(4H)-one (389 mg) as a colorless powder.

Workup

  1. stirringthe mixture was stirred at the same temperature for 1.5 hours
  2. extractionthe mixture was extracted with diethylether
  3. washThe organic layer was washed successively with an aqueous saturated sodium hydrogencarbonate solution and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was triturated in ethyl acetate

Sources & evidence

ORD record
ord-850aa22d3de6463b82a0e825443fb2ea
Source dataset
uspto-grants-2012_05
Patent number
US08188073B2

Reaction notes

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