Acetonitrile → HCID 86727310, compound

HRID 518961Notes

Reaction equation

HRID 518961 reaction equation
[CH3:1][C:2]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][C:5]2[NH:6][C:7](=[O:10])[CH2:8][O:9][C:4]=2[CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH2:22]([O:24][C:25](=[O:29])[CH:26](Br)[CH3:27])[CH3:23].CC#N>CC(C)=O.O>[CH2:22]([O:24][C:25](=[O:29])[CH:26]([N:6]1[C:5]2[CH:11]=[C:12]([N+:13]([O-:15])=[O:14])[C:2]([CH3:1])=[CH:3][C:4]=2[O:9][CH2:8][C:7]1=[O:10])[CH3:27])[CH3:23]

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 11430Potassium CarbonateHCID 79040Ethyl 2-bromopropionateHCID 19908778HCID 19908778, compound

Product 1

HCID 86727310HCID 86727310, compoundYield 112.6%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

To 7-methyl-6-nitro-4H-benzo[1,4]oxazin-3-one (50% purity; 0.870 g, 1.44 mmol) and K2CO3 (1.15 g, 8.36 mmol) in acetone (20 mL) was added 2-bromo-propionic acid ethyl ester (1.5 g, 8.36 mmol) and the mixture was heated at 70° C. for 5 h. The reaction mixture was cooled to ambient temperature and the solvent was removed in vacuo and the residue was dissolved in DCM (15 mL). The solution was washed with water (15 mL), dried over anhydrous Na2SO4, filtered and the filtrate was evaporated in vacuo. The residue was purified by chromatography on silica gel (eluting with 20% EtOAc in petroleum ether) to give a mixture of the title compound as a yellow solid (total 0.5 g crude, 48% desired product as indicated by HPLC at 254 or 220 nm), HPLC (Column: Ultimate XB-C18, 3 um, 50×3.0 mm; Mobile phase: MeCN (0.02% TFA) in water (0.04% TFA), from 30% to 90% within 7 min; Flow rate: 1.5 mL/min; Wavelength: 220 nm) Rt=3.42 min.), which was used directly in the next step.

Workup

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. customthe solvent was removed in vacuo
  3. dissolutionthe residue was dissolved in DCM (15 mL)
  4. washThe solution was washed with water (15 mL)
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. customthe filtrate was evaporated in vacuo
  8. customThe residue was purified by chromatography on silica gel (eluting with 20% EtOAc in petroleum ether)
  9. customto give

Sources & evidence

ORD record
ord-e04feedad10c44c68c81097cb565bad7
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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