Acetic Acid → Ethyl 3-nitro-1H-pyrazole-4-carboxylate

HRID 1426268Notes

Reaction equation

HRID 1426268 reaction equation
B1([O-])OO1.[OH2:5].[OH2:6].O.O.[Na+].C(O)(=O)C.[NH2:14][C:15]1[NH:19][N:18]=[CH:17][C:16]=1[C:20]([O:22][CH2:23][CH3:24])=[O:21]>O>[N+:14]([C:15]1[NH:19][N:18]=[CH:17][C:16]=1[C:20]([O:22][CH2:23][CH3:24])=[O:21])([O-:6])=[O:5]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 81472ethyl 3-amino-1H-pyrazole-4-carboxylateHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate

Product 1

HCID 67962964Ethyl 3-nitro-1H-pyrazole-4-carboxylate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of sodium perborate tetrahydrate (95%, 15.7 g, 96.9 mmol) and acetic acid (60 mL) was heated to 85° C. Ethyl 5-amino-1H-pyrazole-4-carboxylate (3.0 g, 19 mmol) was added, and the mixture was allowed to react at 85° C. for 18 hours. The reaction was then poured into water and extracted with EtOAc. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo; purification via silica gel chromatography (Gradient: 0% to 100% EtOAc in heptane) provided C1. Yield: 1.41 g, 7.62 mmol, 40%. LCMS m/z 184.0 (M−1). 1H NMR (400 MHz, CDCl3) δ 1.39 (t, J=7.2 Hz, 3H), 4.40 (q, J=7.1 Hz, 2H), 8.32 (s, 1H).

Workup

  1. customto react at 85° C. for 18 hours
  2. extractionextracted with EtOAc
  3. dry with materialThe combined organic layers were dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. custompurification via silica gel chromatography (Gradient: 0% to 100% EtOAc in heptane)

Sources & evidence

ORD record
ord-31a330f501804d118985c62b65552ed9
Source dataset
uspto-grants-2015_01
Patent number
US08933095B2

Reaction notes

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