Pyridine → 1-BENZOTHIOPHENE-5-CARBONITRILE

HRID 1983903Notes

Reaction equation

HRID 1983903 reaction equation
[C:1]([Cu])#[N:2].Br[C:5]1[CH:13]=[CH:12][C:8]2[S:9][CH:10]=[CH:11][C:7]=2[CH:6]=1.N1C=CC=CC=1.C(N)CN>CN(C=O)C>[S:9]1[CH:10]=[CH:11][C:7]2[CH:6]=[C:5]([C:1]#[N:2])[CH:13]=[CH:12][C:8]1=2

Participants

6

Reactant 4

HCID 1049PyridineHCID 3301EthylenediamineHCID 27765785-Bromo-1-benzothiopheneHCID 178418546HCID 178418546, compound

Product 1

HCID 27954521-BENZOTHIOPHENE-5-CARBONITRILEYield 92.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of CuCN (86 g, 960 mmol), 5-bromobenzo[b]thiophene (157 g, 723 mmol), pyridine (80 mL) and DMF (1400 mL) was heated at reflux for 14 h. After cooled to 80° C., the reaction mixture was poured into a cold aqueous solution of ethylenediamine (400 mL in 2 L water) cooled by an icebath. The product was extracted with ether (2×1.5 L). The ether layer was washed with brine (1 L), dried (Na2SO4), and concentrated. The residue was recrystallized from CHCl3/Hexanes (50 mL/2000 mL) to give benzo[b]thiophene-5-carbonitrile (106 g, 90%) as a white solid: 1H NMR (300 MHz, CDCl3) δ 8.15 (s, 1H), 7.97 (d, J=8.3 Hz, 1H), 7.61 (d, J=5.4 Hz, 1H), 7.56 (d, J=8.3 Hz, 1H), 7.41 (d, J=5.4 Hz, 1H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 14 h
  3. temperaturecooled by an icebath
  4. extractionThe product was extracted with ether (2×1.5 L)
  5. washThe ether layer was washed with brine (1 L)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customThe residue was recrystallized from CHCl3/Hexanes (50 mL/2000 mL)

Sources & evidence

ORD record
ord-6ecb9cfe0abd4e29a9c88afb1c00ca62
Source dataset
uspto-grants-2009_06
Patent number
US07541357B2

Reaction notes

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