Potassium Carbonate → HCID 59394957, compound

HRID 471893Notes

Reaction equation

HRID 471893 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[OH:10])[C:5]#[N:6].C([O-])([O-])=O.[K+].[K+].Br[CH:18]([CH2:24]Br)[C:19]([O:21][CH2:22]C)=[O:20]>CC(C)=O.CO>[C:5]([C:4]1[CH:7]=[CH:8][C:9]2[O:10][CH:18]([C:19]([O:21][CH3:22])=[O:20])[CH2:24][NH:1][C:2]=2[CH:3]=1)#[N:6]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 97945Ethyl 2,3-dibromopropionateHCID 2712583-Amino-4-hydroxybenzonitrile

Product 1

HCID 59394957HCID 59394957, compoundYield 50.7%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 887MethanolSolvent

Procedure

3-Amino-4-hydroxy-benzonitrile (180 mg, 1.34 mmol) was dissolved in acetone (1.4 mL). To the solution was added K2CO3 (555 mg, 4.02 mmol) and ethyl 2, 3-dibromopropanoate (380 mg, 1.46 mmol). The mixture was heated to reflux for 16 h. After cooling to room temperature the reaction mixture was filtered and concentrated in vacuo to give an oil. The oil was dissolved in methanol and was purified by silica gel chromatography (0-10% dichloromethane/hexanes) to afford methyl 6-cyano-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylate (148 mg, 0.68 mmol). The methyl ester was isolated as methanol was used for loading the compound on silica resulting in transesterification. 1H NMR (400.0 MHz, DMSO-d6) δ 6.98 (dd, J=2.0, 8.2 Hz, 1H), 6.93-6.90 (m, 2H), 6.34 (s, 1H), 5.13 (t, J=3.3 Hz, 1H), 3.66 (s, 3H), 3.50-3.41 (m, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 16 h
  3. filtrationwas filtered
  4. concentrationconcentrated in vacuo
  5. customto give an oil
  6. customwas purified by silica gel chromatography (0-10% dichloromethane/hexanes)

Sources & evidence

ORD record
ord-fdcfb3fa2ab84b67a929e246c0035de2
Source dataset
uspto-grants-2014_01
Patent number
US08633189B2

Reaction notes

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