Ethylene Glycol → 1-[5-(2-Methyl-[1,3]dioxolan-2-yl)-furan-2-ylmethyl]-3-nitro-1H-pyrazole

HRID 2064928Notes

Reaction equation

HRID 2064928 reaction equation
N#N.[N+:3]([C:6]1[CH:10]=[CH:9][N:8]([CH2:11][C:12]2[O:16][C:15]([C:17](=[O:19])[CH3:18])=[CH:14][CH:13]=2)[N:7]=1)([O-:5])=[O:4].[CH2:20](O)[CH2:21][OH:22].CC1C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1.CC(=O)OCC.O>[CH3:18][C:17]1([C:15]2[O:16][C:12]([CH2:11][N:8]3[CH:9]=[CH:10][C:6]([N+:3]([O-:5])=[O:4])=[N:7]3)=[CH:13][CH:14]=2)[O:22][CH2:21][CH2:20][O:19]1

Participants

8

Reactant 4

HCID 174Ethylene GlycolHCID 947NitrogenHCID 6101p-Toluenesulfonic acidHCID 669284331-[5-(3-Nitro-pyrazol-1-ylmethyl)-furan-2-yl]-ethanone

Product 1

HCID 669283961-[5-(2-Methyl-[1,3]dioxolan-2-yl)-furan-2-ylmethyl]-3-nitro-1H-pyrazole

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

In a flame dried round-bottomed flask equipped with a magnetic stir bar and a Dean-Stark apparatus under inert atmosphere (N2), a solution of 1-[5-(3-nitro-pyrazol-1-ylmethyl)-furan-2-yl]-ethanone (1.760 g, 7.48 mmol), ethylene glycol (4.18 mL, 74.98 mmol) and TsOH (14 mg, 0.08 mmol) in toluene (74.8 mL) was heated to reflux for 4 h. The reaction mixture was allowed to cool to rt. Water (125 mL) and EA (25 mL) were added and the aq. phase was extracted with EA (2×50 mL). The combined org. extracts were washed with sat. aq. NaHCO3, dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (60:40 hept-EA) gave the title compound as a yellow oil. TLC: rf (60:40 hept-EA)=022. LC-MS-conditions 02: tR=0.92 min; [M+H]+=280.04. 1H NMR (400 MHz, CDCl3) δ 1.71 (s, 3H), 3.95-4.02 (m, 2H), 4.02-4.09 (m, 2H), 5.36 (s, 2H), 6.33 (d, J=3.3 Hz, 1H), 6.41 (d, J=3.0 Hz, 1H), 6.91 (d, J=2.5 Hz, 1H), 7.48 (d, J=2.3 Hz, 1H).

Workup

  1. customIn a flame dried round-bottomed flask equipped with a magnetic stir bar
  2. temperatureto reflux for 4 h
  3. extractionthe aq. phase was extracted with EA (2×50 mL)
  4. washextracts were washed with sat. aq. NaHCO3
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customthe solvents were removed under reduced pressure
  8. customPurification of the residue by FC (60:40 hept-EA)

Sources & evidence

ORD record
ord-2b90ae82380e4b1b95ccd0fd8805f8ae
Source dataset
uspto-grants-2012_10
Patent number
US08288419B2

Reaction notes

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