Ethyl (2E)-3-(3,4-difluoro-5-hydroxyphenyl)-2-propenoate → Ethyl 3-(3,4-difluoro-5-hydroxyphenyl)propanoate

HRID 602034Notes

Reaction equation

HRID 602034 reaction equation
[F:1][C:2]1[CH:3]=[C:4](/[CH:10]=[CH:11]/[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:5]=[C:6]([OH:9])[C:7]=1[F:8]>C(O)C>[F:1][C:2]1[CH:3]=[C:4]([CH2:10][CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:5]=[C:6]([OH:9])[C:7]=1[F:8]

Participants

3

Reactant 1

HCID 57470569Ethyl (2E)-3-(3,4-difluoro-5-hydroxyphenyl)-2-propenoate

Product 1

HCID 57470570Ethyl 3-(3,4-difluoro-5-hydroxyphenyl)propanoateYield 95%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A 2 L Parr hydrogenation flask was charged with ethyl (2E)-3-(3,4-difluoro-5-hydroxyphenyl)-2-propenoate (91.1 g) and 750 mL of absolute ethanol. The solution was deoxygenated by bubbling nitrogen for 15 minutes. To this was added 10.15 g of catalyst (5% Pd/C—wet) and placed under hydrogen atmosphere (55 psi). After 21 h of stirring, starting material was still present so the reaction was filtered, washed with methanol and DCM and concentrated. The residue was diluted with 550 mL of absolute ethanol and deoxygenated by bubbling nitrogen for 30 minutes. An additional 9.32 g of 10% Pd/C (dry) was added and the reaction placed under hydrogen atmosphere (60 psi) for another 22 h. The reaction was still not complete. The reaction was then filtered as above and the residue was dissolved in 450 mL of ethanol and an additional 10 g of 10% Pd/C (dry) was added and the reaction placed under hydrogen atmosphere (60 psi) for another 20 h. The reaction was then filtered though a pad of Celite and washed with CH3OH and CH2Cl2 and concentrated to get the desired product (86.9 g) in 95% yield.

Workup

  1. customThe solution was deoxygenated
  2. customby bubbling nitrogen for 15 minutes
  3. additionTo this was added 10.15 g of catalyst (5% Pd/C—wet)
  4. filtrationwas filtered
  5. washwashed with methanol and DCM
  6. concentrationconcentrated
  7. additionThe residue was diluted with 550 mL of absolute ethanol
  8. customdeoxygenated
  9. customby bubbling nitrogen for 30 minutes
  10. additionAn additional 9.32 g of 10% Pd/C (dry) was added
  11. customfor another 22 h
  12. filtrationThe reaction was then filtered as above and the residue
  13. dissolutionwas dissolved in 450 mL of ethanol
  14. additionan additional 10 g of 10% Pd/C (dry) was added
  15. customfor another 20 h
  16. filtrationThe reaction was then filtered though a pad of Celite
  17. washwashed with CH3OH and CH2Cl2
  18. concentrationconcentrated

Sources & evidence

ORD record
ord-7f6e86f33a8247d499ee30e795709a59
Source dataset
uspto-grants-2011_03
Patent number
US07902394B2

Reaction notes

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