Hydrochloric Acid → HCID 178496282, compound

HRID 1805508

Reaction equation

HRID 1805508 reaction equation
[N:1]([O-])=O.[Na+].[CH2:5]([O:12][C:13]1[CH:19]=[CH:18][C:16]([NH2:17])=[C:15]([F:20])[CH:14]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.Cl.[CH3:22][O:23][CH2:24][C:25](=[O:31])[CH2:26][C:27]([O:29][CH3:30])=[O:28].CC([O-])=O.[Na+]>O.CO>[CH2:5]([O:12][C:13]1[CH:19]=[CH:18][C:16]([NH:17][N:1]=[C:26]([C:25](=[O:31])[CH2:24][O:23][CH3:22])[C:27]([O:29][CH3:30])=[O:28])=[C:15]([F:20])[CH:14]=1)[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 123500Methyl 4-methoxyacetoacetateHCID 517045Sodium AcetateHCID 114998094-(Benzyloxy)-2-fluoroanilineHCID 23668193Sodium Nitrite

Product 1

HCID 178496282HCID 178496282, compoundYield 94.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of NaNO2 (2.07 g, 30 mmol) in H2O (5 mL) was added dropwise at 0° C. to a mixture of 4-(benzyloxy)-2-fluoroaniline (5.43 g, 25 mmol) and 6 M HCl aqueous solution (25 mL, 150 mmol). After stirring for 15 min, the resulting aqueous solution was added to a suspension of methyl 4-methoxyacetoacetate (3.24 mL, 24 mmol) and NaOAc (12.3 g, 150 mmol) in MeOH (50 mL) pre-cooled at 0° C. The reaction mixture was poured into water and extracted with AcOEt. The extract was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was recrystallized from hexane/AcOEt to give the title compound (8.48 g, 91% yield) as a yellow solid: 1H NMR (300 MHz, CDCl3): δ ppm 3.500 (3H×0.46, s), 3.502 (3H×0.54, s), 3.88 (3H×0.54, s), 3.92 (3H×0.46, s), 4.65 (2H×0.46, s), 4.68 (2H×0.54, s), 5.06 (2H×0.54, s), 5.07 (2H×0.46, s), 6.75-6.86 (2H, m), 7.32-7.44 (5H, m), 7.53 (1H×0.46, t, J=9.0 Hz), 7.76 (1H×0.54, t, J=9.0 Hz), 13.12 (1H×0.46, brs), 15.13 (1H×0.54, brs).

Workup

  1. extractionextracted with AcOEt
  2. washThe extract was washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was recrystallized from hexane/AcOEt

Sources & evidence

ORD record
ord-eebeb4d31cb34ce2aa1335d3535c25a4
Source dataset
uspto-grants-2013_01
Patent number
US08354411B2

Linked notes

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