Sodium Bicarbonate → 5-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazole

HRID 1915812Notes

Reaction equation

HRID 1915812 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2(O)[CH2:13][CH2:12][CH:11]=[CH:10][CH2:9][CH2:8]2)=[C:5]([N+:15]([O-:17])=[O:16])[CH:4]=[N:3]1.COCCN(S(F)(F)F)CCOC.C([O-])(O)=O.[Na+]>C(Cl)Cl.C1COCC1>[C:7]1([C:6]2[N:2]([CH3:1])[N:3]=[CH:4][C:5]=2[N+:15]([O-:17])=[O:16])=[CH:8][CH2:9][CH:10]=[CH:11][CH2:12][CH2:13]1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 86680017(Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol

Product 1

HCID 866800185-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazoleYield 42%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (Z)-1-(1-methyl-4-nitro-1H-pyrazol-5-yl)cyclohept-4-enol (1.35 g, 5.70 mmol) in dry DCM (60 mL) was added dropwise a solution of deoxo-Fluor® (50% in THF, 6.2 mL, 17.1 mmol) and the reaction mixture was stirred at room temperature for 90 min. The mixture was cooled to 0° C. and saturated aqueous NaHCO3 solution (70 mL) was added, dropwise initially, and extracted with DCM (100 mL). The organic layer was separated, dried over MgSO4, and concentrated under reduced pressure. Purification via silica gel column chromatography (15-20% EtOAc/hexane) gave 5-((1E,4Z)-cyclohepta-1,4-dienyl)-1-methyl-4-nitro-1H-pyrazole as a pale yellow oil (523 mg, 42%). 1H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 5.90 (t, J=5.6 Hz, 1H), 5.88-5.79 (m, 1H), 5.71-5.63 (m, 1H), 3.82 (s, 3H), 3.14-3.08 (m, 2H), 2.62-2.55 (m, 2H), 2.44-2.37 (m, 2H).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. extractiondropwise initially, and extracted with DCM (100 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customPurification via silica gel column chromatography (15-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-e224b688cd474d76b404dcf6e874832d
Source dataset
uspto-grants-2013_12
Patent number
US08614206B2

Reaction notes

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