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

HRID 485895Notes

Reaction equation

HRID 485895 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-2329ce697b32429388637bc9496ba260
Source dataset
uspto-grants-1985_08
Patent number
US04537976

Reaction notes

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