Chloro(4-methoxyphenyl)di(propan-2-yl)silane → Allyl(diisopropyl)(4-methoxyphenyl)silane

HRID 1008250Notes

Reaction equation

HRID 1008250 reaction equation
Cl[Si:2]([C:9]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][CH:10]=1)([CH:6]([CH3:8])[CH3:7])[CH:3]([CH3:5])[CH3:4].[CH2:17]([Mg]Cl)[CH:18]=[CH2:19]>C1COCC1>[CH2:19]([Si:2]([C:9]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][CH:10]=1)([CH:6]([CH3:8])[CH3:7])[CH:3]([CH3:5])[CH3:4])[CH:18]=[CH2:17]

Participants

4

Reactant 2

HCID 22666858Chloro(4-methoxyphenyl)di(propan-2-yl)silaneHCID 178418473HCID 178418473, compound

Product 1

HCID 22666856Allyl(diisopropyl)(4-methoxyphenyl)silane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To the crude chloro(4-methoxyphenyl)diisopropylsilane (54.8 g, 214 mmol, 1.0 equiv.) was added THF (335 mL) via cannula under positive argon pressure. The solution was chilled to 0° C. and treated with allylmagnesiumchloride (128 mL, 256 mmol, 2.0 M in THF, 1.2 equiv.). After 3 h at 0° C., the solution was allowed to warm to 23° C. with stirring overnight. The mixture was treated with NH4Clsat'd (50 mL) and the aqueous layer extracted with ether (3×500 mL). The combined organic extracts were washed with brine, dried (MgSO4), filtered, concentrated in vacuo. The crude material was purified by silica gel chromatography (3-5% EtOAc/hexanes) to yield 52.86 g (94%) of a slightly cloudy, viscous oil. This reagent distills at 130° C. at 500 mtorr as a colorless oil. TLC Rf=0.40 (9:1 Hexanes/EtOAc). IR (film) 2942, 2865, 1630, 1595, 1504, 1463, 1277 cm−1. 1H NMR (500 MHz, CDCl3) δ7.32 (d, 2H, J=6.84, C3-H,C7-H), 6.18 (d, 2H, J=6.84, C4-H, C6-H), 5.82 (q, 1H, J=8.5, 8.5, C15-H), 4.88 (d, 1H, J=17.05, C16-Hb), 4.76 (d, 1H, J=9.77, C16-Ha), 1.82 (d, 2H, J=7.32, C14-H), 1.17 (q, 2H, J=7.3, C8-H, C11-H), 0.94 (d, 6H, J=7.3, C9-H, C10-H), 0.90 (d, 6H, J=7.3, C12-H, C13-H). 13C NMR (125 MHz, CDCl3) δ160.51, 136.48, 135.70, 125.78, 113.78, 113.62, 55.09, 19.34, 18.22, 18.17, 17.68, 11.30. Anal. Calcd for C16H26OSi: C, 73.22; H, 9.98; Si, 10.70.

Workup

  1. temperatureto warm to 23° C.
  2. additionThe mixture was treated with NH4Clsat'd (50 mL)
  3. extractionthe aqueous layer extracted with ether (3×500 mL)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude material was purified by silica gel chromatography (3-5% EtOAc/hexanes)
  9. customto yield 52.86 g (94%) of a slightly cloudy, viscous oil
  10. distillationThis reagent distills at 130° C. at 500 mtorr as a colorless oil

Sources & evidence

ORD record
ord-7ae4b9eb1b3d467db917fff72a9ac266
Source dataset
uspto-grants-2004_09
Patent number
US06797819B1

Reaction notes

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