Acetaldehyde → HCID 10729079, compound

HRID 439880Notes

Reaction equation

HRID 439880 reaction equation
C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.[F:21][C:22]1[CH:35]=[CH:34][C:25]([O:26][C:27]2[O:31][C:30]([C:32]#[CH:33])=[CH:29][CH:28]=2)=[CH:24][CH:23]=1.[CH:36](=[O:38])[CH3:37]>C1COCC1>[F:21][C:22]1[CH:35]=[CH:34][C:25]([O:26][C:27]2[O:31][C:30]([C:32]#[C:33][CH:36]([OH:38])[CH3:37])=[CH:29][CH:28]=2)=[CH:24][CH:23]=1

Participants

7

Reactant 5

HCID 177AcetaldehydeHCID 7912DiisopropylamineHCID 2724682Lithium diisopropylamideHCID 10798147HCID 10798147, compoundHCID 178418339Butyllithium

Product 1

HCID 10729079HCID 10729079, compoundYield 80.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Lithium diisopropylamide was generated by the addition of n-butyl lithium (14.2 mL, 35,4 mmol, 2.5M in hexanes) to a stirred -78° C. THF (100 mL) solution as of diisopropylamine (3.58 g, 35.4 mmol) followed by warming to -5° C. (ice/methanol) and stirring for 0.5 hours. To this stirred solution was added the 2-[5-(4-fluorophenoxy)-2-furyl]-ethyne (6.5 g, 32.2 mmol) prepared in step 3 as a THF solution via syringe. The reaction was stirred 0.5 hours and acetaldehyde (3.11 g, 70.8 mmol) was added via syringe, the ice bath was removed, and the reaction warmed to room temperature. Water was added and most of the THF removed in vacuo. The resulting mixture was partitioned between water and ethyl acetate. The combined ethyl acetate layers were dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (30% ether/hexanes) to give 6.39 g (73%) of 4-[5-(4-fluorophenoxy)-2-furyl]-3-butyne-2-ol as a slightly yellow solid. mp(ether/hexanes) 56°-57.5° C. 1H NMR (300 MHz, CDCl3) δ 1.54 (d, 3H, J=7 Hz), 1.88 (d, 1H, J=6 Hz), 4.75 (m, 1H), 5.47 (d, 1H, J=4 Hz), 6.53 (d, 1H, J=4 Hz), 7.04 (m, 4H). MS (DCI/NH3) m/e 247 (M+H)+, 229.

Workup

  1. stirringThe reaction was stirred 0.5 hours
  2. customthe ice bath was removed
  3. additionWater was added and most of the THF
  4. customremoved in vacuo
  5. customThe resulting mixture was partitioned between water and ethyl acetate
  6. dry with materialThe combined ethyl acetate layers were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by chromatography on silica gel (30% ether/hexanes)

Sources & evidence

ORD record
ord-94424eb8f27545ae9b512609308ef499
Source dataset
uspto-grants-1996_05
Patent number
US05516789

Reaction notes

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