2,6-Dichlorobenzaldehyde → HCID 11011981, compound

HRID 895948Notes

Reaction equation

HRID 895948 reaction equation
Cl[C:2]1[CH:9]=[CH:8][CH:7]=[C:6](Cl)[C:3]=1[CH:4]=[O:5].C(N[CH:15]([CH3:17])C)(C)C.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[CH3:31][Si:32]([C:35]#[CH:36])([CH3:34])[CH3:33]>C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[Cu]I.O1CCOCC1>[CH3:31][Si:32]([CH3:34])([CH3:33])[C:35]#[C:36][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([C:17]#[C:15][Si:32]([CH3:34])([CH3:33])[CH3:31])[C:3]=1[CH:4]=[O:5]

Participants

8

Reactant 4

HCID 67372,6-DichlorobenzaldehydeHCID 7912DiisopropylamineHCID 66111Trimethylsilylacetylene2×HCID 83681Tris(1,1-dimethylethyl)phosphine

Product 1

HCID 11011981HCID 11011981, compoundYield 37%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

Following the method described by Buchwald and Fu (Hundertmark, T. et al., Org. Lett. 2000, 12, 1729-1731), samples of 2,6-dichlorobenzaldehyde (3.56 g, 20.4 mmol), Pd(PhCN)2Cl2 (468 mg, 1.22 mmol), and CuI (155 mg, 814 μmol) were placed in a Schlenk flask. Diisopropylamine (6.7 mL), dioxane (30 mL), and P(t-Bu)3 (494 mg, 2.44 mmol) were placed in a Schlenk flask and sparged of oxygen for 10 min, then added to the Schlenk flask. The flask was placed in an oil bath heated to 70° C. After 5 min, (trimethylsilyl)acetylene (7.19 mL, 50.9 mmol) was added and the mixture was stirred at 70° C. for 4 h. Removal of an aliquot and analysis by GC showed mono and di-coupled products in a nearly 1:1 ratio. An additional equivalent of (trimethylsilyl) acetylene (2.9 mL, 20.4 mmol) was added. After 24 h at 70° C., GC analysis showed no mono-coupled product. The mixture was cooled to room temperature, then filtered through a pad of silica. Kugelrohr distillation (110° C., 0.1 Torr) followed by column chromatography (silica, toluene) afforded a yellow oil (2.22 g, 37%): 1H NMR δ0.27 (s, 18H), 7.40-7.43 (m, 1H), 7.51 (d, J=8.0Hz, 2H), 10.63 (s, 1H); 13C NMR δ−0.0, 101.5, 102.5, 125.2, 132.3, 134.4, 137.2, 190.6; FAB-MS obsd 299.1267, calcd 299.1287; Anal Calcd. for C17H22OSi2: C, 68.40; H, 7.43; Found: C, 67.94; H, 7.36.

Workup

  1. customwere placed in a Schlenk flask
  2. customsparged of oxygen for 10 min
  3. additionadded to the Schlenk flask
  4. customThe flask was placed in an oil bath
  5. customRemoval of an aliquot and analysis by GC
  6. waitAfter 24 h at 70° C.
  7. temperatureThe mixture was cooled to room temperature
  8. filtrationfiltered through a pad of silica
  9. distillationKugelrohr distillation (110° C., 0.1 Torr)

Sources & evidence

ORD record
ord-b86bafdc77c243329b3eb3e00a73ad2d
Source dataset
uspto-grants-2005_07
Patent number
US06916982B2

Reaction notes

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