Methyl Ethyl Ketone → Ethyl[(6,7-dichloro-2-hydroxymethylbenzo[b]thien-5-yl)oxy]acetate

HRID 370986Notes

Reaction equation

HRID 370986 reaction equation
[Cl:1][C:2]1[C:3]([OH:14])=[CH:4][C:5]2[CH:9]=[C:8]([CH2:10][OH:11])[S:7][C:6]=2[C:12]=1[Cl:13].Br[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18].C(=O)([O-])[O-].[K+].[K+].CC(=O)CC>CN(C)C=O>[CH2:20]([O:19][C:17](=[O:18])[CH2:16][O:14][C:3]1[C:2]([Cl:1])=[C:12]([Cl:13])[C:6]2[S:7][C:8]([CH2:10][OH:11])=[CH:9][C:5]=2[CH:4]=1)[CH3:21]

Participants

6

Reactant 4

HCID 6569Methyl Ethyl KetoneHCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 132900386,7-Dichloro-5-hydroxy-2-hydroxymethylbenzo[b]thiophene

Product 1

HCID 13290039Ethyl[(6,7-dichloro-2-hydroxymethylbenzo[b]thien-5-yl)oxy]acetateYield 107.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 1.24 g of 6,7-dichloro-5-hydroxy-2-hydroxymethylbenzo[b]thiophene, 0.9 g of ethyl bromoacetate, 0.6 g of potassium carbonate, 25 ml of 2-butanone and 0.5 ml of dimethylformamide is stirred under reflux for 2 hrs. The aqueous layer is extracted twice with 50 ml portions of dichloromethane. The combined organic extracts, are washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated to give a clear oil which crystallizes on standing. Recrystallization of the crude product from acetone-hexane gives 1.8 g of ethyl[(6,7-dichloro-2-hydroxymethylbenzo[b]thien-5-yl)oxy]acetate mp 117°-118.5°.

Workup

  1. temperatureunder reflux for 2 hrs
  2. extractionThe aqueous layer is extracted twice with 50 ml portions of dichloromethane
  3. washThe combined organic extracts, are washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a clear oil which
  8. customcrystallizes
  9. customRecrystallization of the crude product from acetone-hexane

Sources & evidence

ORD record
ord-d5d47b08d52f4d68a4a74b21cf11221e
Source dataset
uspto-grants-1985_07
Patent number
US04528399

Reaction notes

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