Ammonium Acetate → HCID 44185544, compound

HRID 1881769Notes

Reaction equation

HRID 1881769 reaction equation
[CH3:1][S:2][CH:3]([CH3:11])[CH:4]=[CH:5][N:6]1CCCC1.[CH2:12]([O:14][C:15](=[O:27])[C:16](=[CH:23]OCC)[C:17](=O)[C:18]([F:21])([F:20])[F:19])[CH3:13].C([O-])(=O)C.[NH4+]>C(#N)C>[CH2:12]([O:14][C:15](=[O:27])[C:16]1[CH:23]=[C:4]([CH:3]([S:2][CH3:1])[CH3:11])[CH:5]=[N:6][C:17]=1[C:18]([F:19])([F:20])[F:21])[CH3:13]

Participants

5

Reactant 3

HCID 517165Ammonium AcetateHCID 4685753Ethyl 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutanoateHCID 74944121HCID 74944121, compound

Product 1

HCID 44185544HCID 44185544, compoundYield 29.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a dry 50 mL round bottom flask equipped with magnetic stirrer, nitrogen inlet, addition funnel, and thermometer, was charged the 1-(3-methylthiobut-1-enyl)pyrrolidine (5.0 g, 0.0291 mol) and 100 mL of dry acetonitrile. The 2-[1-ethoxymethylidene]-4,4,4-trifluoro-3-oxo-butyric acid ethyl ester (7.0 g, 0.0291 mol) was added dropwise, and the reaction was stirred at room temperature for 1 hour. An aliquot was analyzed by gas chromatography (GC) which indicated that no starting material remained Ammonium acetate (5.0 g, 0.058 mol) was added to the dark red solution and the reaction was heated at reflux for 30 minutes. Cooled and concentrated under vacuum on a rotary evaporator, the crude product was purified by silica gel column chromatography with a gradient of 5% ethyl acetate, 95% hexane to 50% ethyl acetate 50% hexane over 20 minutes to afford 2.5 g of the title compound as a pale yellow oil. 1H NMR (CDCl3): δ 1.42 (t, 3H), 1.62 (d, 3H), 1.96 (s, 3H), 3.94 (q, 1H), 4.43 (q, 2H), 8.08 (s, 1H), and 8.71 (s, 1H).

Workup

  1. customTo a dry 50 mL round bottom flask equipped with magnetic stirrer, nitrogen inlet, addition funnel
  2. additionwas added to the dark red solution
  3. temperaturethe reaction was heated
  4. temperatureat reflux for 30 minutes
  5. temperatureCooled
  6. concentrationconcentrated under vacuum on a rotary evaporator
  7. customthe crude product was purified by silica gel column chromatography with a gradient of 5% ethyl acetate, 95% hexane to 50% ethyl acetate 50% hexane over 20 minutes

Sources & evidence

ORD record
ord-a32fdefdc84c4c7880943fe76476f3c6
Source dataset
uspto-grants-2012_11
Patent number
US08318946B2

Reaction notes

Loading…