Dimethylformamide → Ethyl 6-nitro-3-[(trimethylsilyl)ethynyl]-1-benzothiophene-2-carboxylate

HRID 1425266Notes

Reaction equation

HRID 1425266 reaction equation
CN(C=O)C.[CH3:6][Si:7]([C:10]#[CH:11])([CH3:9])[CH3:8].Br[C:13]1[C:17]2[CH:18]=[CH:19][C:20]([N+:22]([O-:24])=[O:23])=[CH:21][C:16]=2[S:15][C:14]=1[C:25]([O:27][CH2:28][CH3:29])=[O:26]>C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.C(N(CC)CC)C>[N+:22]([C:20]1[CH:19]=[CH:18][C:17]2[C:13]([C:11]#[C:10][Si:7]([CH3:9])([CH3:8])[CH3:6])=[C:14]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[S:15][C:16]=2[CH:21]=1)([O-:24])=[O:23]

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 66111TrimethylsilylacetyleneHCID 67549192Ethyl 3-bromo-6-nitro-1-benzothiophene-2-carboxylate

Product 1

HCID 67549085Ethyl 6-nitro-3-[(trimethylsilyl)ethynyl]-1-benzothiophene-2-carboxylate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

DMF (20 ml), (trimethylsilyl)acetylene (5 ml), triethylamine (10 ml) and bis(triphenylphosphine)palladium (II) dichloride (420 mg, 0.6 mmol) were added to ethyl 3-bromo-6-nitro-1-benzothiophene-2-carboxylate obtained in Example (183b) (794 mg, 2.41 mmol) and copper (I) iodide (12 mg, 0.63 mmol), and the mixture was stirred at 80° C. for one hour. The reaction solution was concentrated under reduced pressure, diluted with ethyl acetate, washed with dilute hydrochloric acid and brine, and dried over anhydrous sodium sulfate. Following concentration under reduced pressure, the residue was purified by silica gel column chromatography (elution solvent: ethyl acetate/hexane=1/10) and recrystallized from an ethyl acetate/hexane solvent, to obtain 110 mg of the title compound as crystals.

Workup

  1. concentrationThe reaction solution was concentrated under reduced pressure
  2. additiondiluted with ethyl acetate
  3. washwashed with dilute hydrochloric acid and brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentration under reduced pressure
  6. customthe residue was purified by silica gel column chromatography (elution solvent: ethyl acetate/hexane=1/10)
  7. customrecrystallized from an ethyl acetate/hexane solvent

Sources & evidence

ORD record
ord-f449ebb9566c4b889df152e08339299c
Source dataset
uspto-grants-2015_01
Patent number
US08927588B2

Reaction notes

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