Ethyl 4-chloroacetoacetate → HCID 86708160, compound

HRID 1465196Notes

Reaction equation

HRID 1465196 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1[NH2:4].[N:10]([O-])=O.[Na+].[Cl:14][CH2:15][C:16](=[O:23])[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19].C([O-])(=O)C.[Na+]>C(Cl)Cl.CC(O)=O.S(=O)(=O)(O)O.CC(O)=O.O.C(Cl)Cl>[Br:1][C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1[N:4]=[N:10][CH:17]([C:16](=[O:23])[CH2:15][Cl:14])[C:18]([O:20][CH2:21][CH3:22])=[O:19]

Participants

10

Reactant 4

HCID 69484Ethyl 4-chloroacetoacetateHCID 2428732-Bromo-4-fluoroanilineHCID 517045Sodium AcetateHCID 23668193Sodium Nitrite

Product 1

HCID 86708160HCID 86708160, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolventHCID 6344DichloromethaneSolventHCID 21922555Acetic acid methylene chlorideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2-bromo-4-fluoroaniline (10 g, 52.6 mmol, 1.0 eq.) in DCM/HOAc (1/1, 160 mL, 0.3M) at 0° C. was added dropwise a precooled solution of sodium nitrite (4.1 g, 57.9 mmol, 1.1 eq.) in conc. sulfuric acid (20 mL). After stirring for 30 min at 0° C. a mixture of ethyl 4-chloroacetoacetate (14.6 mL, 17.8 g, 108 mmol, 1.2 eq.) in HOAc (40 mL) and H2O (80 mL) was added within 5 min. After further 15 min at 0° C. a solution of sodium acetate (72 g, 0.878 mol, 16.7 eq.) in H2O (140 mL) was added slowly. The mixture stirred for 30 min at 0° C. and than 12 h at RT. DCM (200 mL) was added and the organic phase was separated. The aq. phase was extracted with DCM (3×100 mL). The combined organic phase was washed with water, phosphate buffer and subsequent with brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure to give the product ethyl 2-(2-bromo-4-fluoro-phenyl)azo-4-chloro-3-oxo-butanoate as a red solid. MS (ES) C12H11BrClFN2O3 requires: 365. Found: 365/367 (M+H)+.

Workup

  1. additionwas added within 5 min
  2. stirringThe mixture stirred for 30 min at 0° C. and than 12 h at RT
  3. customthe organic phase was separated
  4. extractionThe aq. phase was extracted with DCM (3×100 mL)
  5. washThe combined organic phase was washed with water, phosphate buffer and subsequent with brine
  6. dry with materialThe organic layer was dried over Na2SO4
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-d79399e6f22446e0b7adb55e3b7ccf28
Source dataset
uspto-grants-2015_04
Patent number
US08999982B2

Reaction notes

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