Ethanol → N-methyl-5-nitro-3-pyridin-2-yl-3,4-dihydro-2H-1,4-benzoxazine-3-carboxamide

HRID 589065Notes

Reaction equation

HRID 589065 reaction equation
[N+:1]([C:4]1[C:9]2[NH:10][C:11]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)([C:14]([OH:16])=O)[CH2:12][O:13][C:8]=2[CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2].F[P-](F)(F)(F)(F)F.[CH3:30][N+:31](C)=C(N(C)C)ON1C2N=CC=CC=2N=N1.C(N(CC)C(C)C)(C)C.CN.C(O)C>CN(C)C=O>[CH3:30][NH:31][C:14]([C:11]1([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=2)[NH:10][C:9]2[C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=[CH:7][C:8]=2[O:13][CH2:12]1)=[O:16]

Participants

7

Reactant 5

HCID 702EthanolHCID 6329MethylamineHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 904091095-nitro-3-pyridin-2-yl-3,4-dihydro-2H-1,4-benzoxazine-3-carboxylic acid

Product 1

HCID 90409054N-methyl-5-nitro-3-pyridin-2-yl-3,4-dihydro-2H-1,4-benzoxazine-3-carboxamideYield 42.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

5-Nitro-3-pyridin-2-yl-3,4-dihydro-2H-1,4-benzoxazine-3-carboxylic acid (0.044 g. 0.15 mmol) in N,N-dimethylformamide (3 mL) was combined with N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate [Oakwood #: 023926](160 mg, 0.42 mmol) and N,N-diisopropylethylamine (100 μL, 0.6 mmol) at room temperature. 3.0 M methylamine in ethanol (0.2 mL, 0.6 mmol) was added, and the resulting mixture was stirred for 1 h, at which time the mixture was partitioned between water and ethyl acetate. The organic layer was washed with 1 N HCl, washed with brine, dried over magnesium sulfate, filtered, and concentrated to give crude N-methyl-5-nitro-3-pyridin-2-yl-3,4-dihydro-2H-1,4-benzoxazine-3-carboxamide solid (0.020 g. 30%). LCMS calculated for C15H15N4O4 (M+H)+: m/z=315.1. found: 315.0.

Workup

  1. customwas partitioned between water and ethyl acetate
  2. washThe organic layer was washed with 1 N HCl
  3. washwashed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4858a07b97434552801b35c1f0bacd96
Source dataset
uspto-grants-2016_01
Patent number
US09227985B2

Reaction notes

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