Chlorotrimethylsilane → Ethyl 3-[(trimethylsilyl)oxy]but-2-enoate

HRID 2101666Notes

Reaction equation

HRID 2101666 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].C(N(CC)CC)C.[CH3:17][Si:18](Cl)([CH3:20])[CH3:19]>CCCCCC>[CH2:8]([O:7][C:1](=[O:6])[CH:2]=[C:3]([O:4][Si:18]([CH3:20])([CH3:19])[CH3:17])[CH3:5])[CH3:9]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 8868Ethyl Acetoacetate

Product 1

HCID 54340571Ethyl 3-[(trimethylsilyl)oxy]but-2-enoateYield 90.9%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent2×

Procedure

A solution of 31.9 mL (0.25 mole) of ethyl acetoacetate is stirred in hexane (350 mL) at room temperature. Triethylamine (42 mL, 0.30 mole) is added, followed by dropwise addition of trimethylsilyl chloride (35 mL, 0.276 mole) keeping the internal temperature below 25° C. using a water bath (about 18° C.). The thick white slurry is stirred overnight at room temperature. 200 mL of hexane is then added and the mixture stirred in an ice bath for 1 hour. The mixture is filtered and the solids are washed with 50 mL of cold hexane. Evaporation of the combined filtrate and washings gives 46 g of 3-trimethylsilanyloxy-but-2-enoic acid ethyl ester as a colorless, slightly cloudy oil. This material is used without further purification in the following step.

Workup

  1. customthe internal temperature below 25° C.
  2. custom(about 18° C.)
  3. stirringthe mixture stirred in an ice bath for 1 hour
  4. filtrationThe mixture is filtered
  5. washthe solids are washed with 50 mL of cold hexane
  6. customEvaporation of the combined filtrate and washings

Sources & evidence

ORD record
ord-6a3eff6957a94849b0da44c6bb63e0c6
Source dataset
uspto-grants-2009_08
Patent number
US07572917B2

Reaction notes

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