Ethyl bromoacetate → ethyl 2-(7-bromo-4-fluoro-9-hydroxy-2-methoxy-9H-xanthen-9-yl)acetate

HRID 931604Notes

Reaction equation

HRID 931604 reaction equation
BrBr.Br[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:10][C:11]1[CH:24]=[C:23]2[C:14]([O:15][C:16]3[C:17]([F:28])=[CH:18][C:19]([O:26][CH3:27])=[CH:20][C:21]=3[C:22]2=[O:25])=[CH:13][CH:12]=1.C1COCC1>C(OCC)C.[Zn]>[Br:10][C:11]1[CH:24]=[C:23]2[C:14]([O:15][C:16]3[C:17]([F:28])=[CH:18][C:19]([O:26][CH3:27])=[CH:20][C:21]=3[C:22]2([CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])[OH:25])=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 7748Ethyl bromoacetateHCID 8028TetrahydrofuranHCID 24408BromineHCID 574756397-bromo-4-fluoro-2-methoxy-9H-xanthen-9-one

Product 1

HCID 67383096ethyl 2-(7-bromo-4-fluoro-9-hydroxy-2-methoxy-9H-xanthen-9-yl)acetateYield 100%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 3283Diethyl EtherSolvent

Procedure

Bromine (0.797 ml, 15.47 mmol) was added to a suspension of zinc dust (8.09 g, 124 mmol in diethyl ether (150 ml) at RT. After 5 minutes, ethyl 2-bromoacetate (6.86 ml, 61.9 mmol) was added drop wise over a time period of 20 minutes and the reaction mixture was heated to reflux for 2 hours. 7-bromo-4-fluoro-2-methoxy-9H-xanthen-9-one (10 g, 30.9 mmol) was added in one portion, followed by THF (100 ml) and the reaction mixture was heated to reflux for 3 hours. The reaction mixture was quenched with aqueous saturated NH4Cl solution (100 mL) and EtOAc (100 mL) and stirred 2 hours at RT. The solution was filtered and the organic phase was separated. The solvent was removed under educed pressure to afford ethyl 2-(7-bromo-4-fluoro-9-hydroxy-2-methoxy-9H-xanthen-9-yl)acetate (12.7 g, 30.9 mmol, 100% yield).

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureto reflux for 2 hours
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 3 hours
  5. customThe reaction mixture was quenched with aqueous saturated NH4Cl solution (100 mL) and EtOAc (100 mL)
  6. filtrationThe solution was filtered
  7. customthe organic phase was separated
  8. customThe solvent was removed

Sources & evidence

ORD record
ord-6ffb542995ae45699e5d69cc006943aa
Source dataset
uspto-grants-2016_03
Patent number
US09296759B2

Reaction notes

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