Hexamethylphosphoramide → Dibenzyl 2-methylenepentanedioate

HRID 850308Notes

Reaction equation

HRID 850308 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 92.5%

Procedure

Benzyl acrylate (500 g, 3.0 mol) was heated in an oil bath to 100° C. Heating was stopped and HMPT (10 g, 61 mmol) was added dropwise while maintaining an internal temperature below 140° C. Once addition was complete, the mixture was stirred and cooled to room temperature. A slurry of silica (5:1 Hexane/EtOAc) was added and the mixture was placed in a column containing a plug of dry silica. The column was washed with 1:1 Hexane/EtOAc and the fractions were combined and evaporated to give 450 g of clear light golden liquid. The liquid was distilled under high vacuum (200 μHg) at 185° C. to give 212 g (42%) of a clear and colorless liquid.

Workup

  1. temperatureHeating
  2. temperaturewhile maintaining an internal temperature below 140° C
  3. additionOnce addition
  4. additionA slurry of silica (5:1 Hexane/EtOAc) was added
  5. additioncontaining a plug of dry silica
  6. washThe column was washed with 1:1 Hexane/EtOAc
  7. customevaporated

Sources & evidence

ORD record
ord-242ea15a821449c298c8c21bd1c819fc
Source dataset
uspto-grants-2000_01
Patent number
US06017903

Reaction notes

Loading…