Ethyl formate → diethyl (3E)-2-(hydroxymethylene)-3-phenylpent-3-ene-1,5-dioate

HRID 2297295Notes

Reaction equation

HRID 2297295 reaction equation
[H-].[Na+].[CH:3]([O:5][CH2:6][CH3:7])=[O:4].[C:8]1(/[C:14](/[CH2:21][C:22](OCC)=[O:23])=[CH:15]\[C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1>CCOCC>[OH:23][CH:22]=[C:21](/[C:14](/[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[CH:15]/[C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:3]([O:5][CH2:6][CH3:7])=[O:4]

Participants

5

Reactant 3

HCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 19786724diethyl (2Z)-3-phenylpent-2-ene-1,5-dioate

Product 1

HCID 86586220diethyl (3E)-2-(hydroxymethylene)-3-phenylpent-3-ene-1,5-dioateYield 97%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

A stirred mixture of NaH (158.4 mg, 6.6 mmol) and ethyl formate (1.07 ml, 13.2 mmol) in Et2O (5 ml) were refluxed under argon for 15 min. Diethyl (2Z)-3-phenylpent-2-ene-1,5-dioate in Et2O (5 ml) was added dropwise to the above solution over 5 min at rt. The reaction was heated to reflux for 12 hours. The heterogeneous yellow mixture was diluted with Et2O (100 ml), washed with sat. NH4Cl (40 ml), half sat. NH4Cl (40 ml), brine (20 ml), dried with Na2SO4, filtered, and concentrated under reduced pressure. The product diethyl (3E)-2-(hydroxymethylene)-3-phenylpent-3-ene-1,5-dioate was obtained in 97% yield and could be used without further purification.

Workup

  1. temperaturewere refluxed under argon for 15 min
  2. temperatureThe reaction was heated
  3. temperatureto reflux for 12 hours
  4. washwashed with sat. NH4Cl (40 ml), half sat. NH4Cl (40 ml), brine (20 ml)
  5. dry with materialdried with Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-742fd8209af54ba683bf0d0f91023c8a
Source dataset
uspto-grants-2002_12
Patent number
US06489344B1

Reaction notes

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