Trimethylsilylacetylene → HCID 59180882, compound

HRID 1689602Notes

Reaction equation

HRID 1689602 reaction equation
[CH2:1]([N:3]([C:6]1[CH:11]=[CH:10][C:9](I)=[CH:8][CH:7]=1)[CH2:4][CH3:5])[CH3:2].C(N(C(C)C)CC)(C)C.[CH3:22][Si:23]([C:26]#[CH:27])([CH3:25])[CH3:24]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([N:3]([C:6]1[CH:11]=[CH:10][C:9]([C:27]#[C:26][Si:23]([CH3:25])([CH3:24])[CH3:22])=[CH:8][CH:7]=1)[CH2:4][CH3:5])[CH3:2]

Participants

5

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 621429N,N-Diethyl-4-iodoaniline

Product 1

HCID 59180882HCID 59180882, compound

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

To an oven dried flask fitted with a magnetic stir bar and condenser, Pd(PPh3)4 (207 mg, 0.18 mmol) and cuprous iodide (115 mg, 0.6 mmol) was added and the system was evacuated and back flushed with N2. Dry THF (25 mL) was added, subsequently N,N-diethyl-(4-iodophenyl)amine (1 g, 3.6 mmol in 3 mL THF) and dry degassed diisopropylethylamine (2.5 mL, 14.5 mmol) stirred for 10 min. Trimethylsilylacetylene (0.85 mL, 6 mmol) was added and the mixture was stirred at room temperature for 4 h and then at 80° C. for 30 min. The reaction mixture was cooled to room temperature, poured into ice water and stirred at rt for 1 h. The mixture was extracted with ethyl acetate (50×3), the combined organic layer was washed with saturated ammonium chloride solution and was dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography using hexane/EAC (0-5%) as eluent. Yield: 0.54 g. (61%). IR (neat) 2958, 2857, 2145, 1605, 1515, 1468, 1401 cm−1; 1H NMR (400 MHz, CDCl3) 7.37 (d, J=8.8 Hz, 2H), 6.57 (d, J=8.8 Hz, 2H), 3.37 (q, 7.2 Hz, 4H), 1.19 (t, 6.8 Hz, 6H), 0.32 (s, 9H); 13CNMR (100 MHz, CDCl3) δ 147.41, 133.14, 110.81, 108.66, 106.77, 90.43, 44.09, 12.35.

Workup

  1. customTo an oven dried flask
  2. customfitted with a magnetic stir bar and condenser
  3. customthe system was evacuated
  4. customback flushed with N2
  5. additionDry THF (25 mL) was added
  6. stirringthe mixture was stirred at room temperature for 4 h
  7. waitat 80° C. for 30 min
  8. stirringstirred at rt for 1 h
  9. extractionThe mixture was extracted with ethyl acetate (50×3)
  10. washthe combined organic layer was washed with saturated ammonium chloride solution
  11. dry with materialwas dried over anhydrous magnesium sulfate
  12. customThe solvent was removed by rotary evaporation
  13. customthe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-cf6a174f19db4f389cb4afac2359e6f2
Source dataset
uspto-grants-2012_04
Patent number
US08153446B2

Reaction notes

Loading…