Chlorotrimethylsilane → 1-Ethoxy-1,3-bis(trimethylsiloxy)hexa-1,3-diene

HRID 505665Notes

Reaction equation

HRID 505665 reaction equation
[CH2:1]([O:3][C:4](=[O:11])[CH2:5][C:6](=[O:10])[CH2:7][CH2:8][CH3:9])[CH3:2].C(N(CC)CC)C.C(=O)([O-])O.[Na+].C([N-]C(C)C)(C)C.[Li+].O1CCCC1.Cl[Si:38]([CH3:41])([CH3:40])[CH3:39]>C1(C)C=CC=CC=1.Cl[Si](C)(C)C.O.CCCCCC>[CH2:1]([O:3][C:4]([O:11][Si:38]([CH3:41])([CH3:40])[CH3:39])=[CH:5][C:6]([O:10][Si:38]([CH3:41])([CH3:40])[CH3:39])=[CH:7][CH2:8][CH3:9])[CH3:2]

Participants

10

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 238498Ethyl 3-oxohexanoateHCID 516892Sodium BicarbonateHCID 10997623Lithium diisopropylamide mono(tetrahydrofuran)

Product 1

HCID 729526991-Ethoxy-1,3-bis(trimethylsiloxy)hexa-1,3-dieneYield 193.6%

Reagents, catalysts & solvents 4

HCID 6397ChlorotrimethylsilaneCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8058HexaneSolvent2×

Procedure

3-Oxohexanoic acid ethyl ester (20 mL, 0.13 mol) was dissolved in toluene (100 mL), and the obtained solution was added with triethylamine (28 mL, 0.20 mol) and chlorotrimethylsilane (24 mL, 0.19 mmol), followed by stirring at a room temperature for 4 hours. The reaction mixture was added with hexane (200 mL) and 0.5 mol/L aqueous sodium hydrogencarbonate solution and then, extracted with hexane 3 times. The organic layers were combined, sequentially washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and then evaporated under reduced pressure. The residue was dissolved in tetrahydrofuran (100 mL) and cooled to −78° C. The obtained solution was added with 2.0 mol/L lithiumdiisopropylamide-tetrahydrofuran solution (78 mL, 0.16 mol) followed by stirring at −78° C. for 1 hour. Then, chlorotrimethylsilane (18 mL, 0.14 mol) was added and the reaction mixture was stirred at −78° C. for 8 hours. The reaction mixture was further added with hexane (200 mL) and water and extracted with hexane 3 times. The organic layers were combined, sequentially washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and then evaporated under reduced pressure to obtain 1-ethoxy-1,3-bis(trimethylsiloxy)hexa-1,3-diene (41 g, 100%).

Workup

  1. extractionextracted with hexane 3 times
  2. washsequentially washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customevaporated under reduced pressure
  5. dissolutionThe residue was dissolved in tetrahydrofuran (100 mL)
  6. temperaturecooled to −78° C
  7. stirringby stirring at −78° C. for 1 hour
  8. stirringthe reaction mixture was stirred at −78° C. for 8 hours
  9. extractionextracted with hexane 3 times
  10. washsequentially washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine
  11. dry with materialdried over anhydrous sodium sulfate
  12. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-efa76df7b0e348cfbe60ef2dc66a09fe
Source dataset
uspto-grants-2010_08
Patent number
US07781485B2

Reaction notes

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