Acetic Acid → 3-Acetoxy-2-(4-methoxyphenyl)-6-azabenzo[b]thiophene

HRID 35537Notes

Reaction equation

HRID 35537 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][C:10]2[CH:11]=[N:12][CH:13]=[CH:14][C:15]=2[C:16](OC)=[S:17])=[CH:5][CH:4]=1.[H-].[Na+].[C:22]([OH:25])(=[O:24])[CH3:23]>O1CCCC1.CN(C)C=O>[C:22]([O:25][C:10]1[C:15]2[CH:14]=[CH:13][N:12]=[CH:11][C:16]=2[S:17][C:9]=1[C:6]1[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=1)(=[O:24])[CH3:23]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 24758Sodium hydrideHCID 86742397Methyl 3-(4-methoxyphenyl)methylthiopyridine-4-carboxylate

Product 1

HCID 142776383-Acetoxy-2-(4-methoxyphenyl)-6-azabenzo[b]thiopheneYield 48%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 0.200 g (.69 mmol) of methyl 3-(4-methoxyphenyl)methylthiopyridine-4-carboxylate in 2 mL of dry tetrahydrofuran was added to a suspension of 83 mg (2.1 mmol) of 60% dispersion of sodium hydride in 2 mL of dry N,N-dimethylformamide. The mixture was stirred at room temperature for 3 hours, then poured onto ice water and acidified with glacial acetic acid. The solid material (product) was collected by filtration and the filtrate was extracted with ethyl acetate. The ethyl acetate extract was dried, concentrated and combined with the solid precipitate that had been collected. This material was heated at reflux with 100 mg sodium acetate in 2 mL of acetic anhydride for 2 hours, then was partitioned between ethyl acetate and water. The aqueous layer was washed with two portions of ethyl acetate and the combined extracts were dried and concentrated. The residue was crystallized from methanol to afford 100 mg (48%) of white crystalline material, m.p. 141-142° C.

Workup

  1. additionpoured onto ice water
  2. filtrationThe solid material (product) was collected by filtration
  3. extractionthe filtrate was extracted with ethyl acetate
  4. extractionThe ethyl acetate extract
  5. customwas dried
  6. concentrationconcentrated
  7. customhad been collected
  8. temperatureThis material was heated
  9. temperatureat reflux with 100 mg sodium acetate in 2 mL of acetic anhydride for 2 hours
  10. customwas partitioned between ethyl acetate and water
  11. washThe aqueous layer was washed with two portions of ethyl acetate
  12. customthe combined extracts were dried
  13. concentrationconcentrated
  14. customThe residue was crystallized from methanol

Sources & evidence

ORD record
ord-8f4e2abc12d546a996287a3be0ac6dcc
Source dataset
uspto-grants-1988_08
Patent number
US04767766

Reaction notes

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