Diethyl Ether → 2-Ethoxycarbonyl-3-methoxycarbonyl-but-2-enoic acid ethyl ester

HRID 1410751Notes

Reaction equation

HRID 1410751 reaction equation
[C:1]([O:6][CH3:7])(=[O:5])[C:2]([CH3:4])=O.[C:8]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11].CCOCC>C(OC(=O)C)(=O)C.[Cl-].[Cl-].[Zn+2]>[CH2:17]([O:16][C:8](=[O:15])[C:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])=[C:2]([C:1]([O:6][CH3:7])=[O:5])[CH3:4])[CH3:18]

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 7761Diethyl MalonateHCID 11748Methyl pyruvate

Product 1

HCID 867141132-Ethoxycarbonyl-3-methoxycarbonyl-but-2-enoic acid ethyl esterYield 77.3%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 7918Acetic AnhydrideSolvent

Procedure

A mixture of ZnCl2 (42 g, 308 mmol) in acetic anhydride (100 mL) was stirred at r.t. for 2 h. The resulting solution was decanted, and to this solution was added methyl pyruvate (15.5 mL, 171 mmol) and diethyl malonate (26 mL, 171 mmol). The resulting mixture was heated at 100° C. for 1 h, then left standing at r.t. for 16 h. Ether (250 mL) was added and the mixture was washed with ice water and saturated NaHCO3. The organic layer was dried over MgSO4 and concentrated to give a dark brown oil, which was distilled under reduced pressure to give 32.3 g of the title compound as a yellow oil. 1H NMR (CDCl3, 200 MHz): δ=4.15-4.40 (m, 4H), 3.78 (s, 3H), 2.20 (s, 3H), 1.20-1.40 (m, 6H).

Workup

  1. customThe resulting solution was decanted
  2. temperatureThe resulting mixture was heated at 100° C. for 1 h
  3. waitleft
  4. waitstanding at r.t. for 16 h
  5. washthe mixture was washed with ice water and saturated NaHCO3
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated
  8. customto give a dark brown oil, which
  9. distillationwas distilled under reduced pressure

Sources & evidence

ORD record
ord-2d4da9e01715408d8184d61c7fd3b0df
Source dataset
uspto-grants-2014_12
Patent number
US08921389B2

Reaction notes

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