Ethyl 4,4,4-trifluoroacetoacetate → HCID 178516152, compound

HRID 1673006Notes

Reaction equation

HRID 1673006 reaction equation
C(O[C:4](=[O:12])[CH2:5][C:6](=O)[C:7]([F:10])([F:9])[F:8])C.Cl.[Cl:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[NH:21][NH2:22]>C(O)C>[Cl:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[N:21]1[C:4]([OH:12])=[CH:5][C:6]([C:7]([F:8])([F:9])[F:10])=[N:22]1

Participants

4

Reactant 2

HCID 67793Ethyl 4,4,4-trifluoroacetoacetateHCID 4432872-Chlorophenylhydrazine hydrochloride

Product 1

HCID 178516152HCID 178516152, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Into a 250 mL flask was weighed 5.01 g of 4,4,4-trifluoro-3-oxo-butyric acid ethyl ester, 4.88 g of 2-chlorophenylhydrazine hydrochloride, and 100 mL of ethanol. The resulting solution was heated at 90-950C for 18 h then was concentrated in vacuo to remove ethanol. The residue was washed into a separatory funnel with ethyl acetate and 1 M HCl. The ethyl acetate was separated, washed with brine, was dried, and concentrated in vacuo. The residue was partially purified by silica gel flash chromatography (Jones Flashmaster, 70 g Silica gel, gradient elution from 100% hexanes to 20% ethyl acetate over 30 minutes). Appropriate fractions were combined and concentrated and product was precipitated by addition of excess hexanes. The solid precipitate was collected by filtration and was dried under high vacuum to afford the intermediate 2-(2-Chlorophenyl)-5-trifluoromethyl-2H-pyrazol-3-ol as a tan powder, yield: 3.73 g (52%). 1H NMR (DMSO-d6): δ 12.25 (br s, 1H), 7.72 (d, J=8 Hz, 1H), 7.5-7.65 (m, 3H), 5.94 (s, 1H).

Workup

  1. customInto a 250 mL flask was weighed
  2. temperatureThe resulting solution was heated at 90-950C for 18 h
  3. concentrationthen was concentrated in vacuo
  4. customto remove ethanol
  5. washThe residue was washed into a separatory funnel with ethyl acetate and 1 M HCl
  6. customThe ethyl acetate was separated
  7. washwashed with brine
  8. customwas dried
  9. concentrationconcentrated in vacuo
  10. customThe residue was partially purified by silica gel flash chromatography (Jones Flashmaster, 70 g Silica gel, gradient elution from 100% hexanes to 20% ethyl acetate over 30 minutes)
  11. concentrationconcentrated
  12. customproduct was precipitated by addition of excess hexanes
  13. filtrationThe solid precipitate was collected by filtration
  14. customwas dried under high vacuum

Sources & evidence

ORD record
ord-7fb1fe852a7a45d9ae18568a24ca8b5c
Source dataset
uspto-grants-2011_08
Patent number
US07998995B2

Reaction notes

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