Chloroacetonitrile → 6-Methoxybenzo[b]thiophene-2-carbonitrile

HRID 1822971Notes

Reaction equation

HRID 1822971 reaction equation
CN(C)[C:3](=O)[S:4][C:5]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:6]=1[CH:13]=O.[OH-].[Na+].ClC[C:21]#[N:22]>O.CO>[CH3:12][O:11][C:9]1[CH:8]=[CH:7][C:6]2[CH:13]=[C:3]([C:21]#[N:22])[S:4][C:5]=2[CH:10]=1

Participants

6

Reactant 3

HCID 7856ChloroacetonitrileHCID 14798Sodium HydroxideHCID 23568930HCID 23568930, compound

Product 1

HCID 133482646-Methoxybenzo[b]thiophene-2-carbonitrileYield 46%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

(Ref: Gallagher, T; Pardoe, D. A.; Porter, R.; Tetrahedron Lett.; 2000, 41(28), 5415–5418.) To a solution of S-(2-formyl-5-methoxyphenyl) dimethylthiocarbamate (1.08 g, 4.5 mmol) in water (4 mL) and methanol (8 mL) was added sodium hydroxide (199 mg, 4.9 mmol), this was heated to reflux for 16 hours. The reaction was cooled to room temperature and chloroacetonitrile (0.28 mL, 4.5 mmol) was added in one portion and the mixture the stirred at room temperature for 1 hour. The methanol was removed in vacuo, and water (10 mL) added. The aqueous layer was extracted with diethyl ether (3×20 mL), dried (MgSO4) and the solvent removed in vacuo. The residue was purified by flash chromatography with a gradient of 0–30% ethyl acetate in iso-hexane to give the title compound as a colourless solid (390 mg, 46%); δH (300 MHz, CDCl3) 7.80–7.70 (1H, m, ArH), 7.29 (2H, m, ArH), 7.11–7.01 (1H, m, ArH) and 3.85 (3H, s, OCH3). M+23=212.0. νmax/cm−1 [film] 2213.50 (m).

Workup

  1. temperaturethis was heated
  2. temperatureto reflux for 16 hours
  3. customThe methanol was removed in vacuo, and water (10 mL)
  4. additionadded
  5. extractionThe aqueous layer was extracted with diethyl ether (3×20 mL)
  6. dry with materialdried (MgSO4)
  7. customthe solvent removed in vacuo
  8. customThe residue was purified by flash chromatography with a gradient of 0–30% ethyl acetate in iso-hexane

Sources & evidence

ORD record
ord-ab042a43d97d46b1b98e0963f7129077
Source dataset
uspto-grants-2006_05
Patent number
US07037932B2

Reaction notes

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