Hydrochloric Acid → Methyl 4-[2-(4-fluorophenyl)ethenyl]-3-methoxycarbonylbenzoate

HRID 2228024Notes

Reaction equation

HRID 2228024 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13].C(N(CCCC)CCCC)CCC.[F:29][C:30]1[CH:37]=[CH:36][C:33]([CH:34]=[CH2:35])=[CH:32][CH:31]=1.Cl>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.O>[F:29][C:30]1[CH:37]=[CH:36][C:33]([CH:34]=[CH:35][C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=2[C:12]([O:14][CH3:15])=[O:13])=[CH:32][CH:31]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7622TributylamineHCID 678834-FluorostyreneHCID 2824912Dimethyl 4-bromoisophthalate

Product 1

HCID 53896095Methyl 4-[2-(4-fluorophenyl)ethenyl]-3-methoxycarbonylbenzoateYield 90.1%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent

Procedure

A mixture of dimethyl 4-bromoisophthalate (54.75 g., 200.5 mmol), water (330 ml), tributylamine (55.63 g., 300.7 mmol), 4-fluorostyrene (55.63 g., 300.7 mmol) and bis(triphenylphoshine)palladium(II)chloride (2.81 g., 4.01 mmol) was heated at reflux with stirring under an inert atmosphere for 6 hours. The reaction was cooled to ambient temperature and acidified to pH 2 with 2M HCl (700 ml). The aqueous layer was removed and the residual solid washed with water (2 L), dissolved in dichloromethane (1 L) and passed through a pad of silica, eluting with more dichloromethane (2 L). Evaporation of the dichloromethane gave a solid, which was further washed with iso-hexane (1 L), and dried to give methyl 4-[2-(4-fluorophenyl)ethenyl]-3-methoxycarbonylbenzoate (56.75 g) as a pale yellow solid.

Workup

  1. temperaturewas heated
  2. temperatureat reflux
  3. customThe aqueous layer was removed
  4. washthe residual solid washed with water (2 L)
  5. dissolutiondissolved in dichloromethane (1 L)
  6. washeluting with more dichloromethane (2 L)
  7. customEvaporation of the dichloromethane
  8. customgave a solid, which
  9. washwas further washed with iso-hexane (1 L)
  10. customdried

Sources & evidence

ORD record
ord-12b80344f0364273ad5a776f184b2840
Source dataset
uspto-grants-2002_07
Patent number
US06414145B1

Reaction notes

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