Hexamethylphosphoramide → Dibenzyl 2-methylenepentanedioate

HRID 1602794Notes

Reaction equation

HRID 1602794 reaction equation
[C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)(=[O:4])[CH:2]=[CH2:3].CN(P(N(C)C)(N(C)C)=O)C>>[CH2:3]=[C:2]([CH2:3][CH2:2][C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4])[C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4]

Participants

3

Reactant 2

HCID 12679HexamethylphosphoramideHCID 75617Benzyl acrylate

Product 1

HCID 10947302Dibenzyl 2-methylenepentanedioateYield 52%

Conditions

Temperature
7.5 °C

Procedure

Benzyl acrylate (19.4 g, 120 mmol) was cooled in a two neck 250 ml round bottom flask to approximately 5° C. To this was added dropwise HMPT (2.14 g, 133.1 mmol) at such a rate as to maintain a temperature of 5-10° C. Once addition was complete the ice/water bath was removed and the mixture allowed to warm to room temperature. Stirring was continued overnight. The clear yellow liquid was added directly to a silica gel column (4 cm*40 cm) and eluted with a gradient (19:1-9:1) solvent system (hexane/EtOAc). The fractions containing the desired material were combined and evaporated to give 1 (10.1 g, 52%) as a clear and colorless liquid. TLC Rf 0.26 (9:1, Hex./EtOAc).

Workup

  1. additionOnce addition
  2. customwas removed
  3. temperatureto warm to room temperature
  4. additionThe clear yellow liquid was added directly to a silica gel column (4 cm*40 cm)
  5. washeluted with a gradient (19:1-9:1) solvent system (hexane/EtOAc)
  6. additionThe fractions containing the desired material
  7. customevaporated

Sources & evidence

ORD record
ord-5eeedfcf3776424ebdb606b7f4b76b34
Source dataset
uspto-grants-1999_11
Patent number
US05985855

Reaction notes

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