Trimethylsilylacetylene → HCID 68286487, compound

HRID 1754030Notes

Reaction equation

HRID 1754030 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].C([Mg]Br)C.[CH3:11][O:12][C:13]1[CH:14]=[C:15]([CH:18]=[C:19]([O:21][CH3:22])[CH:20]=1)[CH2:16]Br>C1COCC1.CCOCC>[CH3:22][O:21][C:19]1[CH:18]=[C:15]([CH2:16][C:2]#[C:1][Si:3]([CH3:6])([CH3:5])[CH3:4])[CH:14]=[C:13]([O:12][CH3:11])[CH:20]=1

Participants

6

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 12744903,5-Dimethoxybenzyl BromideHCID 178418443HCID 178418443, compound

Product 1

HCID 68286487HCID 68286487, compoundYield 100.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of ethynyl trimethylsilane (39.1 mL, 277 mmol, 4 equiv) in THF (120 mL) at 0° C. was added ethylmagnesium bromide (3.16 M in Et2O; 87.6 mL, 277 mmol, 4 equiv). The reaction was allowed to warm to room temperature and stirred for 30 min. After 30 min at room temperature, CuBr (9.93 g, 69.2 mmol, 1 equiv) was added and the reaction was allowed to stir at room temperature for an additional 15 min prior to addition of 3,5-dimethoxybenzylbromide (16.0 g, 69.2 mmol, 1 equiv). The resulting mixture was heated to reflux overnight (20 h). The reaction was diluted with Et2O, cautiously quenched with brine, and extracted with Et2O (×2). The combined organic layers were washed with a saturated aqueous solution of NH4Cl, brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The crude mixture was purified by chromatography on SiO2 (EtOAc/hexanes, 1:10) to give 17.2 g (100% yield) of 7 as a pale yellow oil: Rf 0.41 (EtOAc/hexanes, 1:20); IR (neat) 2956, 2898, 2175, 1754, 1596, 1459, 1428, 1204, 1156, 1122, 1101, 839 cm−1; 1H NMR (400 MHz, CDCl3) δ 6.53 (d, 2H, J=2.4 Hz), 6.34 (t, 1 H, J=2.4 Hz), 3.79 (s, 6 H), 3.60 (s, 2H), 0.19 (s, 9 H); 13C NMR (100 MHz, CDCl3) δ 160.8, 138.7, 105.9, 104.0, 98.7, 87.1, 55.3, 26.3, 0.1; HRMS (ESI+) m/z calcd for C14H21O2Si 249.1311, found 249.1287.

Workup

  1. waitAfter 30 min at room temperature
  2. stirringto stir at room temperature for an additional 15 min
  3. temperatureThe resulting mixture was heated
  4. temperatureto reflux overnight (20 h)
  5. customcautiously quenched with brine
  6. extractionextracted with Et2O (×2)
  7. washThe combined organic layers were washed with a saturated aqueous solution of NH4Cl, brine
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe crude mixture was purified by chromatography on SiO2 (EtOAc/hexanes, 1:10)

Sources & evidence

ORD record
ord-4780a4e7d13044b9a8b94277ca1b8721
Source dataset
uspto-grants-2015_10
Patent number
US09169182B2

Reaction notes

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