Methyl Acrylate → methyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}-phenyl)prop-2-enoate

HRID 511721Notes

Reaction equation

HRID 511721 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:25])([F:24])[O:9][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH2:18][CH2:19][C:20]([F:23])([F:22])[F:21])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.C(N(CC)CC)C.[C:33]([O:37][CH3:38])(=[O:36])[CH:34]=[CH2:35]>CN(C=O)C.CC(OC)(C)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[F:24][C:8]([F:25])([O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH2:18][CH2:19][C:20]([F:23])([F:22])[F:21])=[CH:12][CH:11]=1)[C:5]1[CH:6]=[CH:7][C:2](/[CH:35]=[CH:34]/[C:33]([O:37][CH3:38])=[O:36])=[CH:3][CH:4]=1

Participants

7

Reactant 3

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 866765571-Bromo-4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}benzene

Product 1

HCID 86676558methyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}-phenyl)prop-2-enoateYield 65.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
130 °C

Procedure

554 mg (2.469 mmol) of Pd(OAc)2, 2.70 g (7.41 mmol) of dicyclohexyl(2′-methylbuphenyl-2-yl)phosphine, 35 g (82 mmol) of 1-bromo-4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]-methyl}benzene, 17.2 ml (123 mmol) of triethylamine and 14.84 ml (165 mmol) of methyl acrylate are solubilised in 500 ml of DMF and heated to 130° C. After 2 hours, the solution is diluted to room temperature and diluted with 500 ml of TBME. The solution is filtrated over a plug of Hyflo. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Crystallisation from toluene/heptane mixture yields 23 g of methyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]-methyl}-phenyl)prop-2-enoate.

Workup

  1. additionthe solution is diluted to room temperature
  2. filtrationThe solution is filtrated over a plug of Hyflo
  3. washThe organic phase is washed repeatedly with water
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltrated
  6. concentrationconcentrated under reduced pressure
  7. customCrystallisation from toluene/heptane mixture

Sources & evidence

ORD record
ord-46d501efc58a42138336b16dd0f372e9
Source dataset
uspto-grants-2015_08
Patent number
US09097938B2

Reaction notes

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