Triethylamine → 4-Dec-1-ynylbenzaldehyde

HRID 735900Notes

Reaction equation

HRID 735900 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[CH:10]#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19].CCN(CC)CC>C1COCC1.[Cu]I.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:10]([C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 129971-DecyneHCID 707414-Bromobenzaldehyde

Product 1

HCID 578413204-Dec-1-ynylbenzaldehydeYield 88.3%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-bromobenzaldehyde (30.0 g, 162.2 mmol), 1-decyne (26.9 g, 35 mL, 194.6 mmol), CuI (309 mg, 1.62 mmol) and of Et3N (68 mL) in anhydrous THF (450 mL) were added PPh3 (1.7 g, 6.49 mmol) and Pd(OAc)2 (728 mg). The reaction mixture was refluxed under argon for 1 hour. After cooling to rt, the solution was concentrated under reduced pressure and the residual oil was dissolved in hexane (480 mL). The solution was washed with an aqueous solution of HCl (0.1N, 1×), brine (2×), water (2×), dried over MgSO4, filtered and concentrated under reduced pressure to give a brown oil. Purification by chromatography on silicagel (c-Hex/EtOAc 20/1) gave the title compound as a yellow solid (34.7 g, 88%). 1H NMR (CDCl3, 300 MHz) δ 9.97 (s, 1H), 7.78 (d, 2H, J=8.7 Hz), 7.51 (d, 2H, J=8.3 Hz), 2.42 (t, 2H, J=7.0 Hz), 1.67-1.55 (m, 2H), 1.50-1.38 (m, 2H), 1.36-1.21 (m, 8H), 0.87 (m, 31). HPLC (Condition A), Rt: 5.50 min (HPLC purity: 93.2%).

Workup

  1. temperatureThe reaction mixture was refluxed under argon for 1 hour
  2. concentrationthe solution was concentrated under reduced pressure
  3. dissolutionthe residual oil was dissolved in hexane (480 mL)
  4. washThe solution was washed with an aqueous solution of HCl (0.1N, 1×), brine (2×), water (2×)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto give a brown oil
  9. customPurification by chromatography on silicagel (c-Hex/EtOAc 20/1)

Sources & evidence

ORD record
ord-52172f180dfd47759e26c8b3c44771d5
Source dataset
uspto-grants-2009_09
Patent number
US07592477B2

Reaction notes

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