Bromide ion → 5-(3-Nitro-pyrazol-1-ylmethyl)-furan-2-carboxylic acid methyl ester

HRID 2064922Notes

Reaction equation

HRID 2064922 reaction equation
N#N.[N+:3]([C:6]1[NH:10][N:9]=[CH:8][CH:7]=1)([O-:5])=[O:4].[CH3:11][O:12][C:13]([C:15]1[O:16][C:17]([CH2:20]Cl)=[CH:18][CH:19]=1)=[O:14].C([O-])([O-])=O.[K+].[K+].[Br-]>CC(C)=O.CC(=O)OCC.O>[CH3:11][O:12][C:13]([C:15]1[O:16][C:17]([CH2:20][N:9]2[CH:8]=[CH:7][C:6]([N+:3]([O-:5])=[O:4])=[N:10]2)=[CH:18][CH:19]=1)=[O:14]

Participants

9

Reactant 5

HCID 259Bromide ionHCID 947NitrogenHCID 11430Potassium CarbonateHCID 75065Methyl 5-(chloromethyl)-2-furoateHCID 1234193-Nitropyrazole

Product 1

HCID 242256295-(3-Nitro-pyrazol-1-ylmethyl)-furan-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), a solution of 5-nitro-1H-pyrazole (10.95 g, 96.89 mmol) in dry acetone (219 mL) was treated with 5-chloromethyl-furan-2-carboxylic acid methyl ester (17.80 g, 96.89 mmol) followed by K2CO3 (67.61 g, 484.29 mmol) and TBA bromide (6.24 g, 19.37 mmol). The reaction mixture was stirred at rt overnight. Water (500 mL) was added followed by EA (1000 mL). The aq. layer was extracted with EA (2×500 mL) and the combined org. extracts were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (50:50 hept-EA) gave the title compound as a yellow oil. TLC: rf (50:50 hept-EA)=0.26. LC-MS-conditions 02: tR=0.84 min. 1H NMR (400 MHz, CDCl3) δ 3.90 (s, 3H), 5.44 (s, 2H), 6.58 (d, J=3.5 Hz, 1H), 6.93 (d, J=2.5 Hz, 1H), 7.15 (d, J=3.5 Hz, 1H), 7.60 (d, J=2.3 Hz, 1H).

Workup

  1. extractionThe aq. layer was extracted with EA (2×500 mL)
  2. dry with materialextracts were dried over MgSO4
  3. filtrationfiltered
  4. customthe solvents were removed under reduced pressure
  5. customPurification of the residue by FC (50:50 hept-EA)

Sources & evidence

ORD record
ord-afe488df061a4e24a9edf0a9553b48cd
Source dataset
uspto-grants-2012_10
Patent number
US08288419B2

Reaction notes

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