Dichlorodiphenylsilane → 1,1-Diphenyl-1-silacyclo-3-pentene

HRID 1463432Notes

Reaction equation

HRID 1463432 reaction equation
[Mg].[C:2]1([Si:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)(Cl)Cl)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:17]=[CH:18][CH:19]=[CH2:20].[Cl-].[NH4+]>CCOCC.C(O)CO.C1COCC1>[C:2]1([Si:8]2([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[CH2:20][CH:19]=[CH:18][CH2:17]2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 6627DichlorodiphenylsilaneHCID 78451,3-ButadieneHCID 25517Ammonium ChlorideHCID 5462224Magnesium

Product 1

HCID 6025451,1-Diphenyl-1-silacyclo-3-penteneYield 64%

Reagents, catalysts & solvents 3

HCID 174Ethylene GlycolSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

Into a 1000 mL three necked rb flask, equipped with a reflux condenser was placed magnesium powder (26.4 g)(1.1 mol), diphenyldichlorosilane (253 g)(1 mol) and THF (500 mL). The reflux condenser was connected to a refrigeration unit with ethylene glycol cooled at -20° C. circulating. With stirring, 1,3-butadiene (81 g) (1.5 mol, 125 mL) at -78° C. Was transferred to this reaction system via a cannula. The reaction mixture was stirred over 72h. The reaction mixture was hydrolyzed with saturated ammonium chloride solution (100 mL) and 100 ml ether was added. The organic solution was separated. The water layer was washed with ether (2×50 mL). The combined organic solution was dried over anhydrous magnesium sulfate, filtered and the volatile solvents removed by evaporation under reduced pressure. The product was purified by distillation through a 10 cm vacuum jacketed Vigreux column. A fraction, bp 155°-7° C./0.2 mmHg, 154 g, 64% yield was collected. The following spectra properties were observed. 1H NMR (δ)1.97 (d,4H, J=0.94Hz), 6.15(t,2H,J=0.94Hz), 7.44-7.53 (m,6H), 7.67-7.71 (m,4H). 13C NMR (δ) 16.84, 127.90, 129.45, 131.00, 134.67, 135.71, 29Si NMR (δ) 8.51.

Workup

  1. customat -78° C
  2. stirringThe reaction mixture was stirred over 72h
  3. additionwas added
  4. customThe organic solution was separated
  5. washThe water layer was washed with ether (2×50 mL)
  6. dry with materialThe combined organic solution was dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customthe volatile solvents removed by evaporation under reduced pressure
  9. distillationThe product was purified by distillation through a 10 cm vacuum
  10. customA fraction, bp 155°-7° C./0.2 mmHg, 154 g, 64% yield was collected

Sources & evidence

ORD record
ord-c7b054762f0c40a7bf7f4b00f57404cf
Source dataset
uspto-grants-1994_04
Patent number
US05300605

Reaction notes

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