Acetic Anhydride → Ethyl 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutanoate

HRID 2280351Notes

Reaction equation

HRID 2280351 reaction equation
[C:1]([O:4][C:5](=O)C)(=O)[CH3:2].[F:8][C:9]([F:19])([F:18])[C:10](=[O:17])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13].C(OCC)(OCC)OCC>>[CH2:1]([O:4][CH:5]=[C:11]([C:10]([C:9]([F:18])([F:19])[F:8])=[O:17])[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH3:2]

Participants

4

Reactant 3

HCID 7918Acetic AnhydrideHCID 31214Ethyl orthoformateHCID 67793Ethyl 4,4,4-trifluoroacetoacetate

Product 1

HCID 4685753Ethyl 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutanoateYield 84.4%

Conditions

Temperature
65 °C

Procedure

The acetic anhydride (367.6 g, 3.6 moles) is heated to 100-105° C., to which a mixture of crude ethyl trifluoroacetoacetate (˜0.96 mole) and triethyl orthoformate (266.8 g, 1.8 moles) is added drop-wise. The reaction mixture is kept at 100-105° C. for 6 hours. The reaction mixture is cooled to 60-70° C. and then concentrated under vacuum to remove excess acetic anhydride, triethyl orthoformate, and generated ethyl acetate. A pale brown liquid (194.6 g) is obtained. The yield of two steps is 81%.

Workup

  1. additionis added drop-wise
  2. concentrationconcentrated under vacuum
  3. customto remove excess acetic anhydride, triethyl orthoformate

Sources & evidence

ORD record
ord-38e29da44b904956842004ddec2a5b18
Source dataset
uspto-grants-2015_09
Patent number
US09139507B2

Reaction notes

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