Hexamethylphosphoramide → Dibenzyl 2-methylenepentanedioate

HRID 1003175Notes

Reaction equation

HRID 1003175 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>CCOC(C)=O>[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

4

Reactant 2

HCID 12679HexamethylphosphoramideHCID 75617Benzyl acrylate

Product 1

HCID 10947302Dibenzyl 2-methylenepentanedioate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
140 °C

Procedure

Benzyl acrylate (500 g, 3 mol) was heated to 100° C. under an atmosphere of nitrogen. The heating was stopped and HMPT (10 g, 61 mmol) was added dropwise while maintaining an internal temperature of 135-145° C. Once addition was complete the mixture was cooled to room temperature and a slurry of silica with 5:1 Hex/EtOAc was added. The slurry was then transferred to a column containing a plug of dry silica. The column was then washed with 1:1 Hex/EtOAc and the solvent was collected and evaporated. The clear yellow liquid was distilled under high vacuum (200 μHg) to give an initial fraction of 8 g distilling at 45° C. and then the desired product at 180-185° C. (212 g, 42%) as a clear and colorless liquid. 1H NMR (CDCl3) 7.3 ppm (3, 10H); 6.2 ppm (s, 1H); 5.5 ppm (s, 1H); 5.2 ppm (s, 2H); 5.1 ppm (s,2H); 2.6 ppm (m, 4H).

Workup

  1. additionOnce addition
  2. temperaturewas cooled to room temperature
  3. additioncontaining a plug of dry silica
  4. washThe column was then washed with 1:1 Hex/EtOAc
  5. customthe solvent was collected
  6. customevaporated
  7. distillationThe clear yellow liquid was distilled under high vacuum (200 μHg)
  8. customto give an initial fraction of 8 g
  9. distillationdistilling at 45° C.
  10. customat 180-185° C.

Sources & evidence

ORD record
ord-02c84f6c03f341ed9ca01c716bbbc5c4
Source dataset
uspto-grants-2000_04
Patent number
US06046180

Reaction notes

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