Ethyl trifluoroacetate → HCID 19983611, compound

HRID 1460281Notes

Reaction equation

HRID 1460281 reaction equation
[Cl:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]#[CH:11])=[CH:4][CH:3]=1.C([Li])CCC.[F:21][C:22]([F:29])([F:28])[C:23](OCC)=[O:24]>O1CCCC1>[Cl:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]#[C:11][C:23](=[O:24])[C:22]([F:29])([F:28])[F:21])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 9794Ethyl trifluoroacetateHCID 19983625HCID 19983625, compoundHCID 178418339Butyllithium

Product 1

HCID 19983611HCID 19983611, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 2.5 g (11.2 mmol) of 5-(4-chlorophenoxy)-3,3-dimethyl-1-pentyne in 25 ml of anhydrous tetrahydrofuran cooled to -78° C. under a nitrogen atmosphere is added 4.5 ml of 2.5M n-butyllithium in hexanes. The mixture is stirred at -78° C. for 1 hour and then is transferred by canula to a solution of 3.19 g (22.4 mmol) of ethyl trifluoroacetate in 10 ml of tetrahydrofuran cooled to -78° C. After the addition is complete, the reaction is stirred at -78° C. for 0.5 hour, is allowed to warm to 0° C. and then is quenched with saturated ammonium chloride followed by 0.1N hydrochloric acid. The layers are separated and the organic phase is washed with saturated sodium bicarbonate and brine. The organic extract is dried over magnesium sulfate, filtered and evaporated. The residue is subjected to flash chromatography on silica gel using hexane:ethyl ether (93:7) as eluting solvent. The appropriate fractions are combined and evaporated to give a light tan oil: IR (film) 2200, 1710 cm-1 ; NMR (CDCl3) δ1.42 (6H, s), 2.04 (2H, d, J=6.5 Hz), 4.1 (2H, t, J=6.6 Hz), 6.81 (2H, d, J=9.0 Hz), 7.23 (2H, d, J=9.0 Hz)

Workup

  1. temperaturecooled to -78° C
  2. additionAfter the addition
  3. stirringthe reaction is stirred at -78° C. for 0.5 hour
  4. temperatureto warm to 0° C.
  5. customis quenched with saturated ammonium chloride
  6. customThe layers are separated
  7. washthe organic phase is washed with saturated sodium bicarbonate and brine
  8. extractionThe organic extract
  9. dry with materialis dried over magnesium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. washas eluting solvent
  13. customevaporated
  14. customto give a light tan oil

Sources & evidence

ORD record
ord-bb5ff93d29714dd5bc466b90b3f251d4
Source dataset
uspto-grants-1991_12
Patent number
US05070207

Reaction notes

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