Diethyl Ether → 1,1-Diethenyl-2,5-dihydro-1H-silole

HRID 654244Notes

Reaction equation

HRID 654244 reaction equation
[CH:1]([Mg]Br)=[CH2:2].Cl[Si:6]1(Cl)[CH2:10][CH:9]=[CH:8][CH2:7]1.[Cl-].[NH4+].[CH3:14][CH2:15]OCC>C1COCC1>[CH:14]([Si:6]1([CH:1]=[CH2:2])[CH2:10][CH:9]=[CH:8][CH2:7]1)=[CH2:15]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 25517Ammonium ChlorideHCID 1366721,1-Dichloro-1-silacyclo-3-penteneHCID 178418507HCID 178418507, compound

Product 1

HCID 198064641,1-Diethenyl-2,5-dihydro-1H-siloleYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

In a 1 L three neck flask equipped with a Teflon covered magnetic stirring bar, reflux condenser and a pressure equalizing addition funnel. Vinyl magnesium bromide (0.5 mol) in THF 350 mL was placed in the reaction flask. The flask and its contents were cooled to 0° C. in an ice water bath. 1,1-Dichloro-1-silacyclopent-3-ene (Damrauer, R.; Simon, R.; Laporterie, A.; Manuel, G.; Park, Y. T.; Weber, W. P. J. Organomet. Chem., 1990, 391, 7) (11 g, 72 mmol) dissolved in 20 mL of THF was placed in the addition funnel and was added dropwise to reaction flask. The reaction was allowed to slowly warm to room temperature over 6 hours. The reaction mixture was poured into ice cold solution of saturated aqueous ammonium chloride. Ether (200 mL) was added and the organic layer was washed with an equal volume of water (3×). The organic layer was dried over anhydrous calcium chloride, filtered and the volatile organic solvents were removed by distillation through a 15 cm vacuum jacketed Bigreux column at atmospheric pressure. The product was distilled under reduced pressure. A fraction bp 43°-45° C./16 mm Hg, 9.4 g, 95% yield was obtained. 1H NMR: 1.44(d,4H, J=1 Hz), 5.87(t,2H, J=1 Hz), 5.81(dd,2H, J=20 and 3.9 Hz), 6.06(dd,2H, J=14.5 and 3.9 Hz), 6.22(dd,2H, J=20 and 14.5 Hz). 13C NMR: 15.46, 130.71, 134.00, 135.02. 29Si NMR: 1.56. IR: 3040, 3020, 2940, 2885, 1605, 1400, 1200, 1095, 1000., 950, 9430, 815, 795, 725, 690 cm-1. UV nm ζ: 207 (2.5×103). Anal. Calc. for C8H12Si: C, 70.51; H, 8.88. Found: C, 70.96; H, 9.06.

Workup

  1. temperaturereflux condenser
  2. additionaddition funnel
  3. additionwas added dropwise to reaction flask
  4. temperatureto slowly warm to room temperature over 6 hours
  5. washthe organic layer was washed with an equal volume of water (3×)
  6. dry with materialThe organic layer was dried over anhydrous calcium chloride
  7. filtrationfiltered
  8. customthe volatile organic solvents were removed by distillation through a 15 cm vacuum
  9. distillationThe product was distilled under reduced pressure
  10. customA fraction bp 43°-45° C./16 mm Hg, 9.4 g, 95% yield was obtained

Sources & evidence

ORD record
ord-0ac39a9f71a44e26ac11d0af28d953b0
Source dataset
uspto-grants-1992_07
Patent number
US05130390

Reaction notes

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