Ethyl chloroformate → HCID 86700476, compound

HRID 1404831Notes

Reaction equation

HRID 1404831 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:5]([NH2:6])=[C:4]([F:12])[CH:3]=1.[H-].[Na+].Cl[C:16]([O:18][CH2:19][CH3:20])=[O:17]>C1COCC1>[CH2:19]([O:18][C:16]([N:6]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:5]1[C:7]([N+:9]([O-:11])=[O:10])=[CH:8][C:2]([Br:1])=[CH:3][C:4]=1[F:12])=[O:17])[CH3:20]

Participants

5

Reactant 3

HCID 10928Ethyl chloroformateHCID 24758Sodium hydrideHCID 27733814-Bromo-2-fluoro-6-nitroaniline

Product 1

HCID 86700476HCID 86700476, compoundYield 43.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 4-bromo-2-fluoro-6-nitroaniline (1) (0.500 g, 2.12 mmol, 1.00 equiv) in THF (20 mL) was added NaH (0.250 g, 6.40 mmol, 3.00 equiv) portion wise at 0° C. After being stirred for 1 h at RT, ethyl chloroformate (1.00 mL, 10.6 mmol, 5.00 equiv) was added drop wise to the reaction mixture at 0° C. The reaction mixture was heated under reflux temperature for 36 h. After consumption of the starting material (by TLC), the reaction was quenched with saturated NH4Cl solution and extracted with EtOAc (2×100 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to give crude; which was purified by silica gel column chromatography (EtOAc/Hexane 1:4) to furnish compound 2 (0.350 g, 43.0%) as yellow solid.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux temperature for 36 h
  3. customAfter consumption of the starting material (by TLC)
  4. customthe reaction was quenched with saturated NH4Cl solution
  5. extractionextracted with EtOAc (2×100 mL)
  6. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give crude
  10. customwhich was purified by silica gel column chromatography (EtOAc/Hexane 1:4)

Sources & evidence

ORD record
ord-833da824cf4540ae87b739e4a3667829
Source dataset
uspto-grants-2014_12
Patent number
US08916133B2

Reaction notes

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