2-Thiophenecarbonyl chloride → HCID 15124019, compound

HRID 1084868Notes

Reaction equation

HRID 1084868 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[O:7][C:8]2[CH:15]=[CH:14][C:13]([C:16]([CH3:19])([CH3:18])[CH3:17])=[C:12]([OH:20])[C:9]=2[C:10]=1[CH3:11])=[O:5])[CH3:2].[S:21]1[CH:25]=[CH:24][CH:23]=[C:22]1[C:26](Cl)=[O:27].[Al+3].[Cl-].[Cl-].[Cl-]>ClCCCl>[CH2:1]([O:3][C:4]([C:6]1[O:7][C:8]2[C:15]([C:26]([C:22]3[S:21][CH:25]=[CH:24][CH:23]=3)=[O:27])=[CH:14][C:13]([C:16]([CH3:19])([CH3:18])[CH3:17])=[C:12]([OH:20])[C:9]=2[C:10]=1[CH3:11])=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 789282-Thiophenecarbonyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 15124018HCID 15124018, compound

Product 1

HCID 15124019HCID 15124019, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

To a solution of ethyl-3-methyl-4-hydroxy-5-tert-butyl-benzofuran-2-carboxylate 12a (0.760 g, 2.75 mmol) in 30 mL dry (4A sieves) 1,2-dichloroethane at 5° C. under nitrogen was added a solution of thiophene-2-carbonyl-chloride (806 mg, 5.49 mmol) in 5 mL 1,2-dichloroethane followed by the portionwise addition of AlCl3 (0.733 g, 5.59 mmol). The cooling bath was removed and the reaction mixture allowed to warm to room temperature and then refluxed for 1.5 hours. The reaction mixture was then cooled and poured into 100 mL ice cold 2N HCl. The organic layer was removed and the aqueous layer extracted with methylene chloride (3×30 mL). The combined organic layers were washed with 5% NaHCO3 (50 mL), water (50 mL) and saturated NaCl (50 mL) and dried over Na2SO4. Concentration followed by flash chromatography (30% EtOAc in hexane) afforded compound 13 as an oil sufficiently pure for further use; 1H NMR d 1.41 (3H, t, J=6 Hz), 1.55 (9H, s), 2.90 (3H, s), 4.42 (2H, q, J=6 Hz), 7.19 (1H, dd, J=4 Hz), 7.75 (2H, d, J=4 Hz), 7.90 (1H, s).

Workup

  1. customThe cooling bath was removed
  2. temperaturerefluxed for 1.5 hours
  3. temperatureThe reaction mixture was then cooled
  4. additionpoured into 100 mL ice cold 2N HCl
  5. customThe organic layer was removed
  6. extractionthe aqueous layer extracted with methylene chloride (3×30 mL)
  7. washThe combined organic layers were washed with 5% NaHCO3 (50 mL), water (50 mL) and saturated NaCl (50 mL)
  8. dry with materialdried over Na2SO4
  9. concentrationConcentration

Sources & evidence

ORD record
ord-09bfb84b257842a5b992c657d82e2184
Source dataset
uspto-grants-1991_04
Patent number
US05006549

Reaction notes

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