Trifluoroacetic acid → 54376-68-0

HRID 1849811Notes

Reaction equation

HRID 1849811 reaction equation
[CH2:1]([Zn]CC)C.FC(F)(F)C(O)=O.[CH:13]1([C:19]([O:21][CH3:22])=[O:20])[CH2:18][CH2:17][CH:16]=[CH:15][CH2:14]1>ClCCl>[CH:15]12[CH2:1][CH:16]1[CH2:17][CH2:18][CH:13]([C:19]([O:21][CH3:22])=[O:20])[CH2:14]2

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 969263-Cyclohexene-1-carboxylic acid, methyl esterHCID 178418750HCID 178418750, compound

Product 1

HCID 5867200454376-68-0Yield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

To a solution of diethyl zinc (1.0 M in hexanes, 35 mL, 35.00 mmol) in anhydrous dichloromethane (34 mL) was added trifluoroacetic acid (3.99 g, 35.0 mmol) in 17.2 mL anhydrous dichloromethane at 0° C. The reaction mixture was stirred at the same temperature for 1 hour, and then added a solution of diidomethane (9.37 g, 35.00 mmol) in anhydrous dichloromethane (17 mL) at 0° C. The reaction mixture was further stirred at the same temperature for another 1 hour. To this mixture was added a solution of methyl cyclohex-3-enecarboxylate (2.45 g, 17.50 mmol) in anhydrous dichloromethane 17 mL) at 0° C. The resulting mixture was warmed to ambient temperature and further stirred for 4 hours. The mixture was quenched with a saturated solution of ammonium chloride (50 mL) and separated the organic layer. The aqueous layer was extracted with dichloromethane (15 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to dryness. The residue was purified by column chromatography with ethyl acetate in hexanes (30%) to afford the title compound as yellow oil (2.56 g, 95%): 1H NMR (300 MHz, CDCl3) δ 3.64 (s, 3H), 2.31-1.92 (m, 3H), 1.84-1.65 (m, 2H), 1.54 (t, J=12.9 Hz, 1H), 1.19-1.04 (m, 1H), 0.93-0.86 (m, 2H), 0.63-0.55 (m, 1H), 0.05-0.00 (m, 1H).

Workup

  1. stirringThe reaction mixture was further stirred at the same temperature for another 1 hour
  2. stirringfurther stirred for 4 hours
  3. customThe mixture was quenched with a saturated solution of ammonium chloride (50 mL)
  4. customseparated the organic layer
  5. extractionThe aqueous layer was extracted with dichloromethane (15 mL)
  6. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to dryness
  9. customThe residue was purified by column chromatography with ethyl acetate in hexanes (30%)

Sources & evidence

ORD record
ord-a1eb966117bd442eb529e796c18bba9c
Source dataset
uspto-grants-2015_02
Patent number
US08952169B2

Reaction notes

Loading…