Trifluoroacetic acid → HCID 69199163, compound

HRID 2377066Notes

Reaction equation

HRID 2377066 reaction equation
[F:1][C:2]1[CH:13]=[CH:12][C:5]([CH2:6][N:7]2[CH:11]=[CH:10][CH:9]=[CH:8]2)=[CH:4][CH:3]=1.CN(C)[CH:16]=[C:17]([N:23]=[CH:24]N(C)C)[C:18]([O:20][CH2:21][CH3:22])=[O:19].FC(F)(F)C(O)=O>C(O)(=O)C>[F:1][C:2]1[CH:13]=[CH:12][C:5]([CH2:6][N:7]2[C:11]3[CH:16]=[C:17]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[N:23]=[CH:24][C:10]=3[CH:9]=[CH:8]2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 10821140HCID 10821140, compoundHCID 54287818HCID 54287818, compound

Product 1

HCID 69199163HCID 69199163, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of 1-(4-fluorobenzyl)-1H-pyrrole (11.1 g, 63.4 mmol), ethyl 3-dimethylamino-2-(dimethylamino-methyleneamino)-acrylate (14.84 g, 69.7 mmol) [prepared according to W. Kantlehner, F. Wagner, H. Bredereck, Liebigs Ann. Chem. 1980, 344-357] and trifluoroacetic acid (19.4 mL, 253.6 mmol) in acetic acid (80 mL) was stirred for 16 h at ambient temperature. Then the solution was heated to reflux for 4 hr. After cooling down, it was concentrated. The residue was poured into satd. potassium carbonate solution (1000 mL) and extracted with ethyl acetate (3×500 mL). The combined organic extracts were washed with brine (2×500 mL), dried over sodium sulfate, and concentrated. Purification by column chromatography with toluene:acetonitrile (2:1) provided the title compound. (3.6 g, 19% yield). 1H NMR (CDCl3) δ ppm 9.15 (s, 1H), 8.23 (s, 1H), 7.37 (d, 1H, J=3.0 Hz), 7.0-7.11 (m, 4H), 6.83 (d, 1H, J=3.0 Hz), 5.40 (s, 2H), 4.52 (q, 2H, J=7.0 Hz), 1.48 (t, 3H, J=7.0 Hz). LCMS (APCI, M+H+): 299.

Workup

  1. temperatureThen the solution was heated
  2. temperatureto reflux for 4 hr
  3. temperatureAfter cooling down
  4. concentrationit was concentrated
  5. additionThe residue was poured into satd
  6. extractionpotassium carbonate solution (1000 mL) and extracted with ethyl acetate (3×500 mL)
  7. washThe combined organic extracts were washed with brine (2×500 mL)
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated
  10. customPurification by column chromatography with toluene:acetonitrile (2:1)

Sources & evidence

ORD record
ord-bbafc1fb7866468ebe4385fa8472e840
Source dataset
uspto-grants-2008_12
Patent number
US07468375B2

Reaction notes

Loading…