Trimethylsilylacetylene → HCID 17981367, compound

HRID 495220Notes

Reaction equation

HRID 495220 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[CH2:7]([CH:9]([CH2:19][CH2:20][CH2:21][CH3:22])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15](I)=[CH:14][CH:13]=1)[CH3:8]>O1CCCC1.C(N(CC)CC)C.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.[Cu]I>[CH2:7]([CH:9]([CH2:19][CH2:20][CH2:21][CH3:22])[CH2:10][O:11][C:12]1[CH:13]=[CH:14][C:15]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:16][CH:17]=1)[CH3:8]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 17981374HCID 17981374, compound

Product 1

HCID 17981367HCID 17981367, compoundYield 75%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

Tetrakis(triphenylphosphine)palladium(0) (0.52 g, 0.45 mmol) was added to a degassed suspension of trimethylsilyl acetylene (3.00 mL, 2.09 g, 21.2 mmol), 4-(2-ethylhexyloxy)iodobenzene (2) (4.27 g, 12.9mmol) and copper (I) iodide (294 mg, 1.54 mmol) in tetrahydrofuran (20 mL) and triethylamine (30 mL). The mixture was stirred under argon at room temperature for 64.5 h. The solution was filtered through a short plug of silica with dichloromethane as eluent and the solvent removed. The residue was purified by column chromatography over silica with light petroleum as eluent to leave [4-(2-ethylhexyloxy)phenylethynyl]trimethylsilane (3) (2.93 mg, 75%) as a clear, colourless oil. (Found: C, 75.35; H, 9.85. Cl9H30OSi requires C, 75.43; H, 10.0%); ν-max(film)/cm−2156 (C≡C); δH(400 MHz, CDCl3) 0.25 (9 H, s, SiMe3), 0.92 (6 H, m, CH3), 1.30-1.51 (8 H, m, CHCH2CH2CH2CH3 and CHCH2CH3) 1.72 (1 H, OCH2CR), 3.84 (2 H, d, J5, OCH2CH) and 6.82 and 7.40 (4 H, AA′BB′, phenyl H); δc(100.6 MHz, CDCl3) 0.1, 11.1, 14.1, 23.0, 23.8, 29.0, 30.4, 39.3, 70.5, 92.2, 105.3, 114.3, 114.8, 133.4 and 159.6.

Workup

  1. filtrationThe solution was filtered through a short plug of silica with dichloromethane as eluent
  2. customthe solvent removed
  3. customThe residue was purified by column chromatography over silica with light petroleum as eluent

Sources & evidence

ORD record
ord-579ed496138a4b0e9a8eeb11137a7e53
Source dataset
uspto-grants-2009_05
Patent number
US07537842B2

Reaction notes

Loading…