Methyl 4-methoxyacetoacetate → HCID 178496272, compound

HRID 1407160Notes

Reaction equation

HRID 1407160 reaction equation
[F:1][C:2]1([F:13])[O:6][C:5]2[CH:7]=[C:8]([F:12])[C:9]([NH2:11])=[CH:10][C:4]=2[O:3]1.[N:14]([O-])=O.[Na+].[CH3:18][O:19][CH2:20][C:21](=[O:27])[CH2:22][C:23]([O:25][CH3:26])=[O:24].CC([O-])=O.[Na+]>Cl.O.CCO>[CH3:18][O:19][CH2:20][C:21](=[O:27])[C:22](=[N:14][NH:11][C:9]1[C:8]([F:12])=[CH:7][C:5]2[O:6][C:2]([F:1])([F:13])[O:3][C:4]=2[CH:10]=1)[C:23]([O:25][CH3:26])=[O:24]

Participants

8

Reactant 4

HCID 123500Methyl 4-methoxyacetoacetateHCID 517045Sodium AcetateHCID 144057002,2,6-Trifluoro-2H-1,3-benzodioxol-5-amineHCID 23668193Sodium Nitrite

Product 1

HCID 178496272HCID 178496272, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 2,2,6-trifluoro-1,3-benzodioxol-5-amine (4.95 g, 25.9 mmol) in 6 M HCl aqueous solution (25.9 mL) was added a solution of NaNO2 (2.15 g, 31.1 mmol) in water (5.2 mL) at 0° C. To a suspension of methyl 4-methoxy-3-oxobutanoate (3.35 mL, 25.9 mmol) and NaOAc (38.9 g) in EtOH (44 mL) was added the above solution at 0° C. The mixture was stirred at 0° C. for 10 min. The precipitates were collected by filtration, washed with water, dissolved in EtOAc, washed with brine and NaHCO3 aqueous solution, dried over MgSO4, filtered and concentrated in vacuo to yield the title compound (6.31 g, 70% yield) as a red solid: 1H NMR (DMSO-d6, 300 MHz): δ ppm 3.33 (3H, s), 3.82 (3H, s), 4.66 (2H, s), 7.57-7.92 (2H, m), 12.32 (1H, brs).

Workup

  1. additionwas added the above solution at 0° C
  2. filtrationThe precipitates were collected by filtration
  3. washwashed with water
  4. dissolutiondissolved in EtOAc
  5. washwashed with brine and NaHCO3 aqueous solution
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e244e3b24e274428b508f748ecdf6c80
Source dataset
uspto-grants-2014_12
Patent number
US08916566B2

Reaction notes

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