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

HRID 495311Notes

Reaction equation

HRID 495311 reaction equation
[O:1]=[C:2]([CH2:9][CH2:10][CH3:11])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].C(N(CC)CC)C.Cl[Si:20]([CH3:23])([CH3:22])[CH3:21].C(=O)([O-])O.[Na+].C([N-]C(C)C)(C)C.[Li+]>C1(C)C=CC=CC=1.O.CCCCCC.O1CCCC1>[CH2:7]([O:6][C:4]([O:5][Si:20]([CH3:23])([CH3:22])[CH3:21])=[CH:3][C:2]([O:1][Si:20]([CH3:23])([CH3:22])[CH3:21])=[CH:9][CH2:10][CH3:11])[CH3:8]

Participants

10

Reactant 5

HCID 6397Chlorotrimethylsilane2×HCID 8471TriethylamineHCID 238498Ethyl 3-oxohexanoateHCID 516892Sodium BicarbonateHCID 2724682Lithium diisopropylamide

Product 1

HCID 729526991-Ethoxy-1,3-bis(trimethylsiloxy)hexa-1,3-dieneYield 142.6%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Procedure

Ethyl 3-oxohexanoate (20 mL, 0.13 mol) was dissolved in toluene (100 mL), and triethylamine (28 mL, 0.20 mol) and chlorotrimethylsilane (24 mL, 0.19 mol) were added thereto and stirred at room temperature for 4 hours. Hexane (200 mL) and aqueous 0.5 mol/L sodium hydrogencarbonate solution were added to the reaction mixture, and extracted three times with hexane. The organic layers were combined, and washed with aqueous saturated sodium hydrogencarbonate solution and aqueous saturated sodium chloride solution in order, then dried over anhydrous sodium sulfate, and the solvent was evaporated away under reduced pressure. The resulting residue was dissolved in tetrahydrofuran (100 mL), and the solution was cooled to −78° C. Tetrahydrofuran solution of 2.0 mol/L lithium diisopropylamide (78 mL, 0.16 mol) was added to the resulting solution, and stirred at −78° C. for 1 hour, and then chlorotrimethylsilane (18 mL, 0.14 mol) was added thereto and further stirred at −78° C. for 8 hours. Hexane (200 mL) and water were added to the reaction mixture, and extracted three times with hexane. The organic layers were combined, and washed with aqueous 0.5 mol/L sodium hydrogencarbonate solution and aqueous saturated sodium chloride solution in order, then dried over anhydrous sodium sulfate, and the solvent was evaporated away under reduced pressure to obtain 1-ethoxy-1,3-bis(trimethylsiloxy)hexa-1,3-diene (41 g, 100%).

Workup

  1. extractionextracted three times with hexane
  2. washwashed with aqueous saturated sodium hydrogencarbonate solution and aqueous saturated sodium chloride solution in order
  3. dry with materialdried over anhydrous sodium sulfate
  4. customthe solvent was evaporated away under reduced pressure
  5. dissolutionThe resulting residue was dissolved in tetrahydrofuran (100 mL)
  6. temperaturethe solution was cooled to −78° C
  7. stirringstirred at −78° C. for 1 hour
  8. stirringfurther stirred at −78° C. for 8 hours
  9. extractionextracted three times with hexane
  10. washwashed with aqueous 0.5 mol/L sodium hydrogencarbonate solution and aqueous saturated sodium chloride solution in order
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated away under reduced pressure

Sources & evidence

ORD record
ord-320c1008afb84559834d30fce2c894dc
Source dataset
uspto-grants-2009_05
Patent number
US07538241B2

Reaction notes

Loading…