Diethyl Ether → Methyl 3-[(trimethylsilyl)oxy]-2-butenoate

HRID 964479Notes

Reaction equation

HRID 964479 reaction equation
C(N(CC)CC)C.[C:8]([O:14][CH3:15])(=[O:13])[CH2:9][C:10]([CH3:12])=[O:11].Cl[Si:17]([CH3:20])([CH3:19])[CH3:18].CCOCC>C1C=CC=CC=1.[Cl-].[Cl-].[Zn+2]>[CH3:18][Si:17]([CH3:20])([CH3:19])[O:11][C:10]([CH3:12])=[CH:9][C:8]([O:14][CH3:15])=[O:13]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 6397ChlorotrimethylsilaneHCID 7757Methyl acetoacetateHCID 8471Triethylamine

Product 1

HCID 2733746Methyl 3-[(trimethylsilyl)oxy]-2-butenoateYield 83%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolvent

Procedure

A mixture of freshly fused ZnCl2 (1.1 g) and triethylamine (86 mL, 0.62 mol) was stirred for 1 h at room temperature. Methyl acetoacetate (40 mL, 0.37 mol) in benzene (80 mL) was added dropwise, followed by chlorotrimethylsilane (90 mL, 0.72 mol). The mixture was stirred overnight at 40° C. After cooling, ether (500 mL) was added. The mixture was stirred for 1 h and filtered through celite. Volatiles were removed in vacuo. Hexanes (200 mL) were added to the residue which was filtered through celite once again. The filtrate was concentrated to dryness and the residue was distilled through a vigreux column at 79°-82° C. (1.2 mm) to afford 57.6 g (83%) of 1 as a clear oil.

Workup

  1. stirringThe mixture was stirred overnight at 40° C
  2. temperatureAfter cooling
  3. stirringThe mixture was stirred for 1 h
  4. filtrationfiltered through celite
  5. customVolatiles were removed in vacuo
  6. additionHexanes (200 mL) were added to the residue which
  7. filtrationwas filtered through celite once again
  8. concentrationThe filtrate was concentrated to dryness
  9. distillationthe residue was distilled through a vigreux column at 79°-82° C. (1.2 mm)

Sources & evidence

ORD record
ord-fc9ff5a2b9824ec887d9849fc18bfdbc
Source dataset
uspto-grants-1998_06
Patent number
US05770180

Reaction notes

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