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

HRID 1825614Notes

Reaction equation

HRID 1825614 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-e1523dc968614d7e98cd6d4d22375060
Source dataset
uspto-grants-2006_05
Patent number
US07045519B2

Reaction notes

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